Sample records for electrospray characteristic curves

Depending on its coordinates in the parameter space, an electrospray can manifest in one of several known regimes – stable, quasi-stable, transitional-chaotic, and non-axial – that ultimately impact measurement sensitivity and precision. An electrospray operating in cone-jet regime provides large and stable spray current, as well as smaller initial droplets that are prerequisites for higher sensitivity and quality mass spectrometric analyses. However, the dynamic conditions encountered in gradient elution-based liquid separations create difficulties for continuous operation in this regime throughout the analysis. We present a preliminary study aimed at stabilizing the electrospray in the cone-jet regime. On the basis of spray current measurements obtained using solvent conditions typically found in liquid chromatography-mass spectrometry, an improved description of the cone-jet stability island is provided by including transitions to and from the recently described astable regime. Additionally, the experimental conditions in which the astable regime marks the transition between pulsating and cone-jet regimes are further clarified. PMID:17896826

Describes an experiment designed to help students gain a better understanding of the characteristics of various electronic components by incorporating a dual-trace oscilloscope in the X-Y mode in addition to direct observations of phase shifts of various signals into a laboratory exercise. (ZWH)

An experimental study of pulsating electrosprays operated at subambient pressure is reported. The pressure domain that affords stable electrospray operation appears to be limited by the vapor pressure of the liquid. The voltage driving the electrospray is shown to have a logarithmic dependence on pressure. The observed scaling amends the relationship currently used to calculate the electric field at the tip of the meniscus of an electrified liquid. PMID:19997584

An experimental study of sub-ambient pressure electrosprays is reported. The pressure domain that affords stable electrospray operation appears to be limited by the vapor pressure of the liquid. The voltage driving the electrospray is shown to have a logarithmic dependence on the pressure. This scaling amends the relationship currently in use to calculate the electric field at the tip of the meniscus of an electrified liquid

In 1960, E. H. Brown defined a set of characteristiccurves (also known as ideal curves) of pure fluids, along which some thermodynamic properties match those of an ideal gas. These curves are used for testing the extrapolation behaviour of equations of state. This work is revisited, and an elegant representation of the first-order characteristiccurves as level curves of a master function is proposed. It is shown that Brown's postulate—that these curves are unique and dome-shaped in a double-logarithmic p, T representation—may fail for fluids exhibiting a density anomaly. A careful study of the Amagat curve (Joule inversion curve) generated from the IAPWS-95 reference equation of state for water reveals the existence of an additional branch.

Let E be a modular elliptic curve over [symbol, see text], without complex multiplication; let p be a prime number where E has good ordinary reduction; and let Finfinity be the field obtained by adjoining [symbol, see text] to all p-power division points on E. Write Ginfinity for the Galois group of Finfinity over [symbol, see text]. Assume that the complex L-series of E over [symbol, see text] does not vanish at s = 1. If p >/= 5, we make a precise conjecture about the value of the Ginfinity-Euler characteristic of the Selmer group of E over Finfinity. If one makes a standard conjecture about the behavior of this Selmer group as a module over the Iwasawa algebra, we are able to prove our conjecture. The crucial local calculations in the proof depend on recent joint work of the first author with R. Greenberg. PMID:11607752

The behavior of nonisentropic flow behind a propagating blast wave is theoretically studied. Exact solutions, expressed in closed form in terms of elementary functions, are presented for three sets of curved characteristicseind a self-similar, strong blast wave.

A new approach to the development of the item characteristiccurve (ICC), which expresses the functional relationship between the level of performance on a given task and an independent variable that is relevant to the task, is presented. The approach focuses on knowledge states, decision processes, and other circumstances underlying responses to…

A recently developed technique to accurately characterize sub-core scale heterogeneity is applied to investigate the factors responsible for flowrate-dependent effective relative permeability curves measured on core samples in the laboratory. The dependency of laboratory measured relative permeability on flowrate has long been both supported and challenged by a number of investigators. Studies have shown that this apparent flowrate dependency is a result of both sub-core scale heterogeneity and outlet boundary effects. However this has only been demonstrated numerically for highly simplified models of porous media. In this paper, flowrate dependency of effective relative permeability is demonstrated using two rock cores, a Berea Sandstone and a heterogeneous sandstone from the Otway Basin Pilot Project in Australia. Numerical simulations of steady-state coreflooding experiments are conducted at a number of injection rates using a single set of input characteristic relative permeability curves. Effective relative permeability is then calculated from the simulation data using standard interpretation methods for calculating relative permeability from steady-state tests. Results show that simplified approaches may be used to determine flowrate-independent characteristic relative permeability provided flow rate is sufficiently high, and the core heterogeneity is relatively low. It is also shown that characteristic relative permeability can be determined at any typical flowrate, and even for geologically complex models, when using accurate three-dimensional models.

The Cable-Controlled Underwater Recovery Vehicle (CURV) program was begun by NOSC for the specific purpose of developing economical systems to recover test ordnance at NOSC's Long Beach and San Clemente Island test ranges. CURV 3 is the latest in this series of tethered, unmanned, remotely controlled vehicles and its present capabilities far exceed the original CURV 1. Originally conceived for use as a search and recovery vehicle, CURV has evolved into a versatile and easily adaptable multipurpose work vehicle capable of performing search and recovery tasks as well as pursuing test, evaluation, exploration, and work projects. Basically, CURV is a composite of integrated subsystems including such items as propulsion, search and navigation, optics, hydraulics, and tools. Because it is unmanned and does not require life support or other complex support systems, CURV is able to perform most undersea tasks more economically and efficiently than maned systems. Also, since it is powered and controlled from the surface, CURV has a continuous, unlimited operating capability. Under emergency conditions, the vehicle can operate to 10,000-foot depths. CURV can be easily transported to any spot in the world. Upon arrival of the vehicle, control van, cable, and support gear can be mounted on a suitable ship of opportunity.

A closed non-linear set of equations is obtained based on the guiding center fluid model to describe steady-state magnetron operation. Spoke charge effects are included self-consistently, by introducing a mean-field approximation so that the effective AC potential preserves the geometric similarity with the vacuum solutions. New characteristic equations, relating the anode current 1 and the RF power P to the applied DC voltage V at given RF frequency, are obtained. Previously obtained V-I equations disagree with experiments in that (a) anode current and RF power go to zero when the resonance condition V = V{sub s} is met, (b) the operation voltage V is a double-valued function of the current I; there exist two nearly symmetric operation points around V{sub s} at the same current I. Yet magnetrons, and the related crossed-field amplifiers, are known to exhibit stable operation with single valued V-I characteristics well below V{sub s}. Although zero gain at synchronism applies to other microwave devices (TWT`s, FEL`s), experimental results and particle simulations of crossed field devices suggest otherwise. The new formulas show reasonable agreement with experiments.

As the typical building blocks of metamaterials, the cut wire and the split ring resonator have been extensively studied in recent years. Besides them, the space-filling curve-based metamaterials are receiving great attentions because of their intrinsic subwavelength and multi-bands characteristics. In this work, we have investigated experimentally and numerically the electromagnetic characteristics of such Hilbert curve metamaterial in the microwave frequency regime and found a deeply subwavelength magnetic resonance supported by the fractal pattern and featuring the wavelength-to-size ratio more than 20. The subwavelength electromagnetic properties of the Hilbert curve will be beneficial to realize high-performance metamaterials.

An electrospray device includes an electrospray emitter adapted to receive electrospray fluid; an extractor plate spaced from the electrospray emitter and having at least one aperture; and a power supply for applying a first voltage between the extractor plate and emitter for generating at least one Taylor cone emission through the aperture to create an electrospray plume from the electrospray fluid, the extractor plate as well as accelerator and shaping plates may include a porous, conductive medium for transporting and storing excess, accumulated electrospray fluid away from the aperture.

Sound water management is essential for effectively producing nursery crops. Understanding substrate water availability is a critical component to managing irrigation properly. The objective of this paper is to report a method for generating moisture characteristiccurves of soilless substrate tha...

The effect of heating conditions on the crust color formation was investigated during the baking of white bread. The surface temperatures were monitored with thermocouples attached to the inside surface of the loaf pan cover. The trace of the surface color in the L(*)a(*)b(*) color coordinate system is defined as the characteristic coloring curve. The overall baking process was classified into the following four stages based on the characteristic coloring curve: i) pre-heating (surface temperature < 110 °C), ii) Maillard reaction (110-150 °C), iii) caramelization (150-200 °C), and iv) over-baking (surface temperature>200 °C). A linear relationship was observed between the L(*) decrease and the increase in weight loss of a sample at each oven air temperature. The L(*) value appeared to be suitable as an indicator to control the surface color by baking conditions. PMID:21307578

POD curves are typically constructed as statistical models of responses to known characteristics of the POD demonstration samples. MIL-HDBK-1823A provides some guidance in choosing the number of samples - viz. at least 40 targets for tests that provide a quantitative response (â) and 60 for binary responses (hit/miss) - but says little about the size range or how they should be placed within that range. Here we report on how the number of targets, their size range, and their distribution (uniform, skewed left or right) with respect to a true POD vs. size relationship influences the POD curve that is estimated from these targets. From the parameter estimates we compute confidence bounds to quantity statistical uncertainty. The work is for binary response data and is based on a novel simulation method for computing the confidence bounds which would prohibitively time-consuming using conventional Monte Carlo methods.

The therapy operating characteristic (TOC) curve, developed in the context of radiation therapy, is a plot of the probability of tumor control versus the probability of normal-tissue complications as the overall radiation dose level is varied, e.g., by varying the beam current in external-beam radiotherapy or the total injected activity in radionuclide therapy. This paper shows how TOC can be applied to chemotherapy with the administered drug dosage as the variable. The area under a TOC curve (AUTOC) can be used as a figure of merit for therapeutic efficacy, analogous to the area under an ROC curve (AUROC), which is a figure of merit for diagnostic efficacy. In radiation therapy, AUTOC can be computed for a single patient by using image data along with radiobiological models for tumor response and adverse side effects. The mathematical analogy between response of observers to images and the response of tumors to distributions of a chemotherapy drug is exploited to obtain linear discriminant functions from which AUTOC can be calculated. Methods for using mathematical models of drug delivery and tumor response with imaging data to estimate patient-specific parameters that are needed for calculation of AUTOC are outlined. The implications of this viewpoint for clinical trials are discussed. PMID:27175376

Characteristiccurve approaches for linking parameters from the generalized partial credit model were examined for cases in which common (anchor) items are calibrated separately in two groups. Three of these approaches are simple extensions of the test characteristiccurve (TCC), item characteristiccurve (ICC), and operating characteristic curve…

Ambient desorption/ionization mass spectrometry (ADI-MS) is an attractive method for direct analysis with applications in homeland security, forensics, and human health. For example, low-temperature plasma probe (LTP) ionization was successfully used to detect, e.g., explosives, drugs, and pesticides directly on the target. Despite the fact that the field is gaining significant attention, few attempts have been made to classify ambient ionization techniques based on their ionization characteristics and performance compared to conventional ionization sources used in mass spectrometry. In the present study, relative ionization efficiencies (RIEs) for a large group of compound families were determined with LTP-Orbitrap-MS and compared to those obtained with electrospray ionization mass spectrometry (ESI-MS) and atmospheric pressure chemical ionization mass spectrometry (APCI-MS). RIEs were normalized against one reference compound used across all methods to ensure comparability of the results. Typically, LTP analyte ionization through protonation/deprotonation (e.g., 4-acetamidophenol) was observed; in some cases (e.g., acenaphthene) radicals were formed. Amines, amides, and aldehydes were ionized successfully with LTP. A benefit of LTP over conventional methods is the possibility to successfully ionize PAHs and imides. Here, the studied model compounds could be detected by neither APCI nor ESI. LTP is a relatively soft ionization method because little fragmentation of model compounds was observed. It is considered to be an attractive method for the ionization of low molecular weight compounds over a relatively wide polarity range. PMID:23134531

A new JSC Mars-1 particle size distribution is used to establish soil moisture characteristic and soil freezing characteristiccurves that are needed for modeling bulk (Darcy) vapor flow and soil freezing in the variably saturated subsurface of Mars.

The Receiver Operating Characteristiccurve (ROC) has long been used in medical applications to compare screening and diagnostic methods. As the threshold used by any screening or diagnostic method is changed, the operating characteristics of the method, such as the number of true positive and false negative determinations changes as well. The ROC curve is one way to characterize the changes in order to compare different methods. This definition, however, is difficult to apply to chemical and biological sensors detecting the release of a toxic agent given that there is more than one ROC curve. There is a continuum of ROC curves corresponding to a continuum of release levels. A new definition of ROC curves has been adopted for chemical and biological sensors which will reduce the continuum of curves to a single curve. This paper presents a methodology to estimate ROC curves using this new definition.

In most item response theory models a particular mathematical form is assumed for all item characteristiccurves, e.g., a logistic function. It could be desirable, however, to estimate the shape of the item characteristiccurves without prior restrictive assumptions about its mathematical form. We have developed a practical method of estimating…

Soil hydrophobicity presents a major challenge for the future, as it reduces both plant-available water and irrigation efficiency, and can increase flooding hazards and erosion. A collaborative research project has been set up in the UK to study hydrophobicity over a wide range of length scales. At core scale, we are investigating the wetting behaviour of water repellent soils in order to model percolation through hydrophobic pore spaces. To that end, water retention measurements were carried out on both wettable and forcibly-wetted water-repellent soils collected from three locations in England and Wales. The data were then fitted with both the commonly used Van Genuchten model and an alternative model from PoreXpert, a software program that analyses and models porous materials. The Van Genuchten model fits a curve to the data using parameters related to air entry suction, irreducible water content and pore size distribution. By contrast, PoreXpert uses a Boltzmann-annealed simplex to find a best-fit curve based on parameters directly related to the void structure of the soil: the size of the voids, the shape of the void size distribution, and how the voids are connected to each other. Both Van Genuchten and PoreXpert fit the experimental data well, but where Van Genuchten forces an S-shaped curve that can mask small variations, PoreXpert gives a closer fit of no pre-defined shape that captures subtle differences between data points. This allows us to calculate differences in the effective pore and throat size distributions, and provides a mechanistic framework from which to model additional hydrologic behaviour in water repellent soil. Simulations of capillary induced wetting based on these mechanistic postulates are then compared to wicking experiments at the core scale, which can then be upscaled and applied to other soils.

Using a simple UV LED-excited ruby fluorescence measurement system, we demonstrate that it is easily possible to obtain unbiased detection limits, despite the system deliberately having non-linear response function and non-Gaussian noise. Even when the noise precision model is heteroscedastic, but otherwise only roughly linear, the receiver operating characteristic (ROC) method readily yields results that are in accordance with a priori canonical specifications of false positives and false negatives at the detection limit. The present work demonstrates that obtaining unbiased detection limits is not abstruse and need not be mathematically complicated. Rather, detection limits continue to serve a useful purpose as part of the characterization of chemical measurement systems.

Measuring the I-V characteristics of a transistor constitutes an important step in an introductory electronics course. We demonstrate the use of a digital oscilloscope with a USB connection to perform a measurement of the characteristiccurves with no additional custom circuitry. The setup is presented alongside the open-source software that allows the signal acquisition and analysis of the results.

The influence of power semiconductor characteristic in Pulse-width-modulation (PWM) inverter on the magnetic hysteresis curve in silicon steel is discussed through the measured magnetic hysteresis curves. The magnetic hysteresis curve of PWM inverter-fed silicon steel has a lot of minor loops as closed loops and open loops, which make an influence on the iron loss. Two shapes of minor loops are found to be caused by the voltage shifts and they are derived from the on-voltage of the semiconductors in PWM inverter circuit. Therefore, it is concluded that the power-semiconductor characteristic in PWM inverter makes an influence on the magnetic hysteresis curve in silicon steel.

The soil water characteristiccurve, h(theta), can be used to estimate a variety of parameters in unsaturated soils. One practical application of h(theta) is its use by DRAINMOD, a drainage model that has been widely used in shallow water table regions, to determine the water table depth–drainage v...

The purpose of this study was to assess the model fit of a 2PL through comparison with the nonparametric item characteristiccurve (ICC) estimation procedures. Results indicate that three nonparametric procedures implemented produced ICCs that are similar to that of the 2PL for items simulated to fit the 2PL. However for misfitting items,…

Moisture characteristiccurves (MCC) relate the water content (') in a substrate to the matric potential ('m) at a given tension or height (h). Most techniques for developing MCC are not well-suited coarse substrates such as those composed of bark used in container nursery substrates. The objectiv...

Under item response theory, the characteristiccurve methods (Haebara and Stocking-Lord methods) are used to link two ability scales from separate calibrations. The linking methods use their respective criterion functions that can be defined differently according to the symmetry- and distribution-related schemes. The symmetry-related scheme…

A simple device for developing moisture characteristic data curves, the submersible pressure outflow cell, was modified for application to rock core at matric potentials of 0 to -0.5 megapascals (MPa) and possibly to -1.0 Mpa. An automated system was developed to continuously and simultaneously collect data from many cells, obtain sorption and desorption characteristiccurves to provide hysteretic information, and data from multi-step outflow experiments. The latter can be used to estimate unsaturated hydraulic conductivity. The system has resolved many of the problems inherent in standard measurement techniques. Model simulation of imbibition using the hysteretic data collected are in close agreement with laboratory measurements of imbibition, data collected are in close agreement with laboratory measurements of imbibition, suggesting the moisture characteristic data correctly describes the core properties.19 refs., 4 figs.

Pump manufacturers do not normally provide the characteristiccurves of their pumps working as turbines. Therefore, establishing a correlation between the performances of direct (pump) and reverse (turbine) modes is essential in selecting the proper machine. In this paper, several centrifugal pumps (N{sub s} < 60 (m, m{sup 3}/s)) were tested as turbines. Using experimental data, some relations were derived to predict the best efficiency point of a pump working as a turbine, based on pump hydraulic characteristics. Validity of the presented method was shown using some referenced experimental data. Two equations were presented to estimate the complete characteristiccurves of centrifugal pumps as turbines based on their best efficiency point. Deviations of suggested method from experimental data were considered and discussed. Finally, a procedure was presented for selecting a suitable pump to work as a turbine in a small hydro-site. (author)

Numerical models of geologic storage of carbon dioxide (CO2)in brine-bearing formations use characteristiccurves to represent theinteractions of non-wetting-phase CO2 and wetting-phase brine. When aproblem includes both injection of CO2 (a drainage process) and itssubsequent post-injection evolution (a combination of drainage andwetting), hysteretic characteristiccurves are required to correctlycapture the behavior of the CO2 plume. In the hysteretic formulation,capillary pressure and relative permeability depend not only on thecurrent grid-block saturation, but also on the history of the saturationin the grid block. For a problem that involves only drainage or onlywetting, a non-hysteretic formulation, in which capillary pressure andrelative permeability depend only on the current value of the grid-blocksaturation, is adequate. For the hysteretic formulation to be robustcomputationally, care must be taken to ensure the differentiability ofthe characteristiccurves both within and beyond the turning-pointsaturations where transitions between branches of the curves occur. Twoexample problems involving geologic CO2 storage are simulated withTOUGH2, a multiphase, multicomponent code for flow and transport codethrough geological media. Both non-hysteretic and hysteretic formulationsare used, to illustrate the applicability and limitations ofnon-hysteretic methods.The first application considers leakage of CO2from the storage formation to the ground surface, while the secondexamines the role of heterogeneity within the storageformation.

To determine the characteristiccurve of the radiographic screen/film systems in a short focal spot-film distance, the inverse square sensitometric method was modified by changing the radiation intensity with two kinds of filters. The characteristiccurves obtained in the two exposure series with these two kinds of filters were overlapped to obtain a complete one. The characteristiccurve thus obtained was almost the same as the one obtained by the original inverse square sensitometric method. The accuracy of the characteristiccurves obtained by the modified method was well-reflected in the clinical radiographs. PMID:3962729

A systematic study was performed to investigate the accuracy and precision attained by four methods for determining the characteristiccurve of radiographic screen/film systems. The four methods include: inverse square sensitometry, KVP adjusted bootstrap sensitometry step-wedge bootstrap sensitometry, and step wedge attenuation sensitometry. The inverse square method was used as the reference standard for accuracy. The extent of and the sources of the inaccurcies involved when using the alternative methods is discussed.

Methods for linking item response theory (IRT) parameters are developed for attitude questionnaire responses calibrated with the generalized graded unfolding model (GGUM). One class of IRT linking methods derives the linking coefficients by comparing characteristiccurves, and three of these methods---test characteristiccurve (TCC), item…

The Lick AGN Monitoring Project targeted 13 nearby Seyfert 1 galaxies with the intent of measuring the masses of their central black holes using reverberation mapping. The sample includes 12 galaxies selected to have black holes with masses roughly in the range 10{sup 6}-10{sup 7} M {sub sun}, as well as the well-studied active galactic nucleus (AGN) NGC 5548. In conjunction with a spectroscopic monitoring campaign, we obtained broadband B and V images on most nights from 2008 February through 2008 May. The imaging observations were carried out by four telescopes: the 0.76 m Katzman Automatic Imaging Telescope, the 2 m Multicolor Active Galactic Nuclei Monitoring telescope, the Palomar 60 inch (1.5 m) telescope, and the 0.80 m Tenagra II telescope. Having well-sampled light curves over the course of a few months is useful for obtaining the broad-line reverberation lag and black hole mass, and also allows us to examine the characteristics of the continuum variability. In this paper, we discuss the observational methods and the photometric measurements, and present the AGN continuum light curves. We measure various variability characteristics of each of the light curves. We do not detect any evidence for a time lag between the B- and V-band variations, and we do not find significant color variations for the AGNs in our sample.

The presently performance-evaluated format, in which a high-gain curved-channel microchannel plate (M2MCP) has a spherical concave input face and a plane output face, allows the input face of the MCP (1) to match such curved focal surfaces as that of a Rowland-circle spectrometer mounting, while (2) having a high-resolution plane readout array in proximity focus with the output face. This MCP has been evaluated in a discrete-anode multicathode microchannel array detector system. The saturated modal gain was found to be inversely proportional to the length/diameter ratio of the channels and directly proportional to the applied MCP voltage.

The improvement of the contrast ratio of flexible liquid crystal displays (LCDs) fabricated using plastic substrates in a curved state is an important problem to achieve high-quality flexible LCDs. In this study, we evaluated the distributions of in-plane phase retardation and slow axis direction of polycarbonate substrates and the effects of curvature on the electro-optical properties of flexible LCDs. As a result, we clarified that the polycarbonate substrates have high uniformity in the in-plane phase retardation and slow axis direction, and that the change in the phase retardation of the polycarbonate substrate caused by the curvature deformation has a small effect on the electro-optical characteristics of flexible LCDs. We successfully achieved a high contrast ratio of 1042:1 by fabricating the device using polycarbonate substrates. This result indicates that it is possible to realize high-quality images in flexible LCDs fabricated using polycarbonate substrates even in the curved state.

Task-based medical image quality is typically measured by the degree to which a human observer can perform a diagnostic task in a psychophysical human observer study. During a typical study, an observer is asked to provide a numerical score quantifying his confidence as to whether an image contains a diagnostic marker or not. Such scores are then used to measure the observers' diagnostic accuracy, summarized by the receiver operating characteristic (ROC) curve and the area under ROC curve. These types of human studies are difficult to arrange, costly, and time consuming. In addition, human observers involved in this type of study should be experts on the image genre to avoid inconsistent scoring through the lengthy study. In two-alternative forced choice (2AFC) studies, known to be faster, two images are compared simultaneously and a single indicator is given. Unfortunately, the 2AFC approach cannot lead to a full ROC curve or a set of image scores. The aim of this work is to propose a methodology in which multiple rounds of the 2AFC studies are used to re-estimate an image confidence score (a.k.a. rating, ranking) and generate the full ROC curve. In the proposed approach, we treat image confidence score as an unknown rating that needs to be estimated and 2AFC as a two-player match game. To achieve this, we use the ELO rating system, which is used for calculating the relative skill levels of players in competitor-versus-competitor games such as chess. The proposed methodology is not limited to ELO, and other rating methods such as TrueSkill™, Chessmetrics, or Glicko can be also used. The presented results, using simulated data, indicate that a full ROC curve can be recovered using several rounds of 2AFC studies and that the best pairing strategy starts with the first round of pairing abnormal versus normal images (as in the classical 2AFC approach) followed by a number of rounds using random pairing. In addition, the proposed method was tested in a pilot human

The precision and accuracy achieved in the measurement of characteristiccurves for radiographic screen/film systems is quantitatively investigated for three techniques: inverse square, kVp bootstrap, and step-wedge bootstrap. Precision of all techniques is generally better than +/- 1.5% while the agreement among all intensity-scale techniques is better than 2% over the useful exposure latitude. However, the accuracy of the sensitometry will depend on several factors, including linearity and energy dependence of the calibration instrument, that may introduce larger errors. Comparisons of time-scale and intensity-scale methods are made and a means of measuring reciprocity law failure is demonstrated. PMID:6877185

High temperature superconducting (HTS) maglev technology is becoming more and more mature, and many key technologies have been deeply studied. However, the transition curve plays a key role in HTS maglev system, and related studies have not been carried out. In this paper series of simulations were conducted to test the lateral and vertical vibration of HTS maglev when passing through curves. Two magnetic guideways, of which one has transition curves but the other does not, are designed to test the vibration characteristics of a mini HTS maglev model running though curves. Results show that after adding transition curves between straight line and circular curve the vibration of HTS maglev model in lateral and vertical directions are all weakened in different degrees. It proves that adding transition curve into HTS maglev system is favorable and necessary.

For deep excavation pits that require the pumping of confined groundwater, a combination of a retaining wall and dewatering with large-diameter wells is usually adopted during excavation to improve safety. Since a retaining wall has a much lower hydraulic conductivity than the surrounding material in the aquifer, blocking of seepage to prolong the seepage path of the groundwater outside of the pit is effective. The retaining walls used during excavation dewatering cause hydraulic head drawdown inside the pit much faster than outside the pit. Thus, difference in hydraulic head between inside and outside of the pit increases. To investigate the mechanism of the blocking effect, numerical simulation using the finite difference method (FDM) was conducted to analyze the effects of pumping in the pit. The FDM results show that drawdown varies along the depth of the confined aquifer. The influence factors of drawdown inside and outside the pit include insertion depth of retaining walls, anisotropy of a confined aquifer and screen length of pumping wells. In addition, FDM results also show that the drawdown-time curve can be divided into four stages: in Stage I, drawdown inside the pit is very small and outside the pit it is almost zero; in Stage II, drawdown increases quickly with time; in Stage III, the drawdown curve is parallel to the Cooper-Jacob curve on semi-log axes; and in Stage IV, the drawdown becomes constant. These characteristics of the drawdown curve under the blocking effect of a retaining wall in an aquifer provide a way of estimating hydrogeological parameters according to pumping test results.

Receiver operating characteristiccurve (ROC) analysis was used to investigate the ability of early numeracy curriculum-based measures (EN-CBM) administered in preschool to predict performance below the 25th and 40th percentiles on a quantity discrimination measure in kindergarten. Areas under the curve derived from a sample of 279 students ranged…

In this paper a new approach is presented based on evolutionary polynomial regression (EPR) for modelling of soil-water characteristiccurve in unsaturated soils. EPR is an evolutionary data mining technique that generates a transparent and structured representation of the behaviour of a system directly from data. This method can operate on large quantities of data in order to capture nonlinear and complex relationships between variables of the system. It also has the additional advantage that it allows the user to gain insight into the behaviour of the system. Results from pressure plate tests carried out on clay, silty clay, sandy loam, and loam are used for developing and validating the EPR model. The model inputs are the initial void ratio, initial gravimetric water content, logarithm of suction normalised with respect to atmospheric air pressure, clay content, and silt content. The model output is the gravimetric water content corresponding to the assigned input suction. The EPR model predictions are compared with the experimental results as well as the models proposed by previous researches. The results show that the proposed approach is very effective and robust in modelling the soil-water characteristiccurve in unsaturated soils. The merits and advantages of the proposed approach are highlighted.

Reported for the first time are receiver operating characteristic (ROC) curves constructed to describe the performance of a sorbent-coated disk, planar solid phase microextraction (PSPME) unit for non-contact sampling of a variety of volatiles. The PSPME is coupled to ion mobility spectrometers (IMSs) for the detection of volatile chemical markers associated with the presence of smokeless powders, model systems of explosives containing diphenylamine (DPA), 2,4-dinitrotoluene (2,4-DNT) and nitroglycerin (NG) as the target analytes. The performance of the PSPME-IMS was compared with the widely accepted solid-phase microextraction (SPME), coupled to a GC-MS. A set of optimized sampling conditions for different volume containers (1–45 L) with various sample amounts of explosives, were studied in replicates (n = 30) to determine the true positive rates (TPR) and false positive detection rates (FPR) for the different scenarios. These studies were obtained in order to construct the ROC curves for two IMS instruments (a bench-top and field-portable system) and a bench top GC-MS system in low and high clutter environments. Both static and dynamic PSPME sampling were studied in which 10–500 mg quantities of smokeless powders were detected within 10 min of static sampling and 1 min of dynamic sampling.

The three fundamental constitutive relations that describe fluid flow, strength, and deformation behavior of variably saturated soils are the soil-water retention curve (SWRC), hydraulic conductivity function (HCF), and suction-stress characteristiccurve (SSCC). Until recently, the interrelations among the SWRC, HCF, and SSCC have not been well established. This work sought experimental confirmation of interrelations among these three constitutive functions. Results taken from the literature for six soils and those obtained for 11 different soils were used. Using newly established analytical relations among the SWRC, HCF, and SSCC and these test results, the authors showed that these three constitutive relations can be defined by a common set of hydromechanical parameters. The coefficient of determination for air-entry pressures determined independently using hydraulic and mechanical methods is >0.99, >0.98 for the pore size parameter, and 0.94 for the residual degree of saturation. One practical implication is that one of any of the four experiments (axis-translation, hydraulic, shear-strength, or deformation) is sufficient to quantify all three constitutive relations.

Soil water repellency (SWR) is a phenomenon that influences many soil hydrologic processes such as reduction of infiltration, increase in overland flow, and enhanced preferential flow. SWR has been observed in various soil types and textures, and the degree of SWR is greatly controlled by soil moisture content and levels of organic matter and clay. One of the key topics in SWR research is how to describe accurately the seasonal and temporal variation of SWR with the controlling factors such as soil moisture, organic matter, and clay contents for soil profiles with natural organic carbon gradients. In the present study, we summarize measured SWR data for soil profiles under different land uses and vegetation in Japan and New Zealand, and compared these with literature data. We introduce the contact angle-based evaluation of SWR and predictive models for soil water repellency characteristiccurves, in which the contact angle is a function of the moisture content. We also discuss a number of novel concepts, including i) the reduction in the contact angle with soil-water contact time to describe the time dependence of SWR, ii) the relationship between the contact angles from the measured scanning curves under controlled wetting and drying cycles, and iii) the initial contact angles measured by the sessile drop method.

Microaneurysms (MAs) are the first manifestations of the diabetic retinopathy (DR) as well as an indicator for its progression. Their automatic detection plays a key role for both mass screening and monitoring and is therefore in the core of any system for computer-assisted diagnosis of DR. The algorithm basically comprises the following stages: candidate detection aiming at extracting the patterns possibly corresponding to MAs based on mathematical morphological black top hat, feature extraction to characterize these candidates, and classification based on support vector machine (SVM), to validate MAs. Feature vector and kernel function of SVM selection is very important to the algorithm. We use the receiver operating characteristic (ROC) curve to evaluate the distinguishing performance of different feature vectors and different kernel functions of SVM. The ROC analysis indicates the quadratic polynomial SVM with a combination of features as the input shows the best discriminating performance.

The objective of this study is to benchmark a four-engine clustered nozzle base flowfield with a computational fluid dynamics (CFD) model. The CFD model is a three-dimensional pressure-based, viscous flow formulation. An adaptive upwind scheme is employed for the spatial discretization. The upwind scheme is based on second and fourth order central differencing with adaptive artificial dissipation. Qualitative base flow features such as the reverse jet, wall jet, recompression shock, and plume-plume impingement have been captured. The computed quantitative flow properties such as the radial base pressure distribution, model centerline Mach number and static pressure variation, and base pressure characteristiccurve agreed reasonably well with those of the measurement. Parametric study on the effect of grid resolution, turbulence model, inlet boundary condition and difference scheme on convective terms has been performed. The results showed that grid resolution had a strong influence on the accuracy of the base flowfield prediction.

The main aim of this paper is determine the centrifugal fan with forward curved blades aerodynamic characteristics based on numerical modeling. Three variants of geometry were investigated. The first, basic "A" variant contains 12 blades. The geometry of second "B" variant contains 12 blades and 12 semi-blades with optimal length [1]. The third, control variant "C" contains 24 blades without semi-blades. Numerical calculations were performed by CFD Ansys. Another aim of this paper is to compare results of the numerical simulation with results of approximate numerical procedure. Applied approximate numerical procedure [2] is designated to determine characteristics of the turbulent flow in the bladed space of a centrifugal-flow fan impeller. This numerical method is an extension of the hydro-dynamical cascade theory for incompressible and inviscid fluid flow. Paper also partially compares results from the numerical simulation and results from the experimental investigation. Acoustic phenomena observed during experiment, during numerical simulation manifested as deterioration of the calculation stability, residuals oscillation and thus also as a flow field oscillation. Pressure pulsations are evaluated by using frequency analysis for each variant and working condition.

The potential distribution in the curved quadrupole is exactly characterized by the Laplace equation, and an approximate solution to the Laplace equation is calculated. We represent the Laplace equation under the coordinates named minimal rotation frame (MRF) and derive an expression on the hexapole and octopole superposition. Our conclusion is in agreement with the results by the numerical (SIMION) method. Based on the Poincare-Lighthill-Kuo (PLK) method reported in our previous work, the nonlinear effects of ion motion are investigated in detail. The frequency shift of ion motion can be well eliminated by coupling the hexapole component with a positive octopole component, and the transmission efficiency of ions is found to decrease dramatically with the increase of the ionic kinetic energy in the z-direction. Furthermore, the transmission characteristics of ions are discussed with regards to the phase-space theory. The results show that the centrifugally introduced axis shift is mainly responsible for the ion losses. A modified direct current (dc) voltage supply pattern is hence proposed to compensate for this effect.

The relationship of red clay particle with water is an important factor to produce geological disaster and environmental damage. In order to reduce the role of adsorbed water of red clay in WuHan, Ionic Soil Stabilizer (ISS) was used to treat the red clay. Soil Moisture Equipment made in U.S.A was used to measure soil-water characteristiccurve of red clay both in natural and stabilized conditions in the suction range of 0-500kPa. The SWCC results were used to interpret the red clay behavior due to stabilizer treatment. In addition, relationship were compared between the basic soil and stabilizer properties such as water content, dry density, liquid limit, plastic limit, moisture absorption rate and stabilizer dosages. The analysis showed that the particle density and specific surface area increase, the dehydration rate slows and the thickness of water film thins after treatment with Ionic Soil Stabilizer. After treatment with the ISS, the geological disasters caused by the adsorbed water of red clay can be effectively inhibited.

Background: The purpose of this study was to determine a score on the Obsessive Compulsive Scale (OCS) from the Child Behavior Checklist (CBCL) to screen for obsessive compulsive disorder (OCD) in children and to rigorously test the specificity and sensitivity of a single cutpoint. Methods: A receiver operating characteristic (ROC) curve analysis…

Blossom blight forecasting is an important aspect of fire blight, caused by Erwinia amylovora, management for both apple and pear. A comparison of the forecast accuracy of two common fire blight forecasters, MARYBLYT and Cougarblight, was performed with receiver operating characteristic (ROC) curve ...

After entering 21st century, we already had two big tsunami disasters associated with Mw9 earthquakes in Sumatra and Japan. To mitigate the damages of tsunami, the numerical simulation technology combined with information technologies could provide reliable predictions in planning countermeasures to prevent the damage to the social system, making safety maps, and submitting early evacuation information to the residents. Shallow water equations are still solved not only for global scale simulation of the ocean tsunami propagation but also for local scale simulation of overland inundation in many tsunami simulators though three-dimensional model starts to be used due to improvement of CPU. One-dimensional shallow water equations are below: partial bm{Q}/partial t+partial bm{E}/partial x=bm{S} in which bm{Q}=( D M )), bm{E}=( M M^2/D+gD^2/2 )), bm{S}=( 0 -gDpartial z/partial x-gn2 M|M| /D7/3 )). where D[m] is total water depth; M[m^2/s] is water flux; z[m] is topography; g[m/s^2] is the gravitational acceleration; n[s/m1/3] is Manning's roughness coefficient. To solve these, the staggered leapfrog scheme is used in a lot of wide-scale tsunami simulator. But this scheme has a problem that lagging phase error occurs when courant number is small. In some practical simulation, a kind of diffusion term is added. In this study, we developed two wide-scale tsunami simulators with different schemes and compared usual scheme and other schemes in practicability and validity. One is a total variation diminishing modification of the MacCormack method (TVD-MacCormack method) which is famous for the simulation of compressible fluids. The other is the Cubic Interpolated Profile (CIP) method with characteristiccurve equations transformed from shallow water equations. Characteristiccurve equations derived from shallow water equations are below: partial R_x±/partial t+C_x±partial R_x±/partial x=∓ g/2partial z/partial x in which R_x±=√{gD}± u/2, C_x±=u± √{gD}. where u

A compacted clay liner (test pad) was constructed and instrumented with volumetric water content and soil matric potential sensors to determine soil water characteristiccurves (SWCC) and hydraulic conductivity (k) functions. Specifically, the compacted clay liner was subjected to an infiltration cycle during a sealed double ring infiltrometer (SDRI) test followed by a drying cycle. After the drying cycle, Shelby tube samples were collected from the compacted clay liner and flexible wall permeability (FWP) tests were conducted on sub-samples to determine the saturated hydraulic conductivity. Moreover, two computer programs (RETC and UNSAT-H) were utilized to model the SWCCs and k-functions of the soil based on obtained measurements including the volumetric water content, the soil matric potential, and the saturated hudraulic conductivity (ks). Results obtained from the RETC program (s, r, α, n and ks) were ingested into UNSAT-H program to calculate the movement of water (rate and location) through the compacted clay liner. Although a linear wetting front (location of water infiltration as a function of time) is typically utilized for SDRI calculations, the use of a hyperbolic wetting front is recommended as a hyperbolic wetting front was modeled from the testing results. The suggested shape of the wetting front is associated with utilization of the desorption SWCC instead of the sorption SWCC and with relatively high values of ks (average value of 7.2E-7 cm/sec) were measured in the FWP tests while relatively low values of ks (average value of 1.2E-7 cm/sec) were measured in the SDRI test.

The stress [crack damage stress ( σ cd) and uniaxial compressive strength ( σ c)] and strain characteristics [maximum total volumetric strain ( ɛ cd), axial failure strain ( ɛ af)], porosity ( n) and elastic constants [elastic modulus ( E) and Poisson's ratio ( ν)] and their ratios were coordinated with the existence of two different types (type 1 and type 2) of volumetric strain curve. Type 1 volumetric strain curve has a reversal point and, therefore, σ cd is less than the uniaxial compressive strength ( σ c). Type 2 has no reversal point, and the bulk volume of rock decreases until its failure occurs (i.e., σ cd = σ c). It is confirmed that the ratio between the elastic modulus ( E) and the parameter λ = n/ ɛ cd strongly affects the crack damage stress ( σ cd) for both type 1 and type 2 volumetric strain curves. It is revealed that heterogeneous carbonate rock samples exhibit different types of the volumetric strain curve even within the same rock formation, and the range of σ cd/ σ c = 0.54-1 for carbonate rocks is wider than the range (0.71 < σ cd/ σ c < 0.84) obtained by other researchers for granites, sandstones and quartzite. It is established that there is no connection between the type of the volumetric strain curve and values of n, E, σ cd, ν, E/(1 - 2 ν), M R = E/ σ c and E/ λ. On the other hand, the type of volumetric strain curve is connected with the values of λ and the ratio between the axial failure strain ( ɛ af) and the maximum total volumetric strain ( ɛ cd). It is argued that in case of small ɛ af/ ɛ cd-small λ, volumetric strain curve follows the type 2.

We compile and analyse long-term (≈10 yr) submillimetre (submm - 1.3, 0.87, 0.43 mm) wavelength light curves of the Galactic Centre black hole, Sagittarius A*. The 0.87 and 0.43 mm data are taken from the literature, while the majority of the 1.3 mm light curve is from previously unpublished SMA and CARMA data. We show that on minute to a few hour time-scales, the variability is consistent with a red noise process with a 230 GHz power-spectrum slope of β =2.3^{+0.8}_{-0.6} at 95 per cent confidence. The light curve is decorrelated (white noise) on long (month to year) times. We measure a transition time between red and white noise of τ = 8_{-4}^{+3} h at 230 GHz at 95 per cent confidence, with consistent results at 345 and 690 GHz. This corresponds to ≈10 orbital times or ≈1 inflow (viscous) time at R = 3Rs, a typical radius producing the 230 GHz emission as measured by very long baseline interferometry and found in theoretical accretion flow and jet models. This time-scale is shorter (longer) than those measured by some analyses of radio (near-infrared) light curves. It is roughly consistent with the analogous time-scale inferred in studies of quasar optical light curves after accounting for the difference in emission radius. We find evidence that the submm variability persists at least down to the innermost stable circular orbit, if not the event horizon. These results can be compared quantitatively with similar analyses at different wavebands to test for connections between the variability mechanisms, and with light curves from theoretical models of accreting black holes.

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... must be obtained from the applicable sampling plan tables. (c) The curves show the ability of the... Plan. An examination of this table reveals that there is one single and one double sampling plan that... double sampling plan that requires the initial inspection of 228 individual containers. The lot will...

... must be obtained from the applicable sampling plan tables. (c) The curves show the ability of the... Plan. An examination of this table reveals that there is one single and one double sampling plan that... double sampling plan that requires the initial inspection of 228 individual containers. The lot will...

... must be obtained from the applicable sampling plan tables. (c) The curves show the ability of the... Plan. An examination of this table reveals that there is one single and one double sampling plan that... double sampling plan that requires the initial inspection of 228 individual containers. The lot will...

The flow duration curve is a signature catchment characteristic that depicts graphically the relationship between the exceedance probability of streamflow and its magnitude. This curve is relatively easy to create and interpret, and is used widely for hydrologic analysis, water quality management, and the design of hydroelectric power plants (among others). Several mathematical expressions have been proposed to mimic the FDC. Yet, these efforts have not been particularly successful, in large part because available functions are not flexible enough to portray accurately the functional shape of the FDC for a large range of catchments and contrasting hydrologic behaviors. Here, we extend the work of Vrugt and Sadegh (2013) and introduce several commonly used models of the soil water characteristic as new class of closed-form parametric expressions for the flow duration curve. These soil water retention functions are relatively simple to use, contain between two to three parameters, and mimic closely the empirical FDCs of 430 catchments of the MOPEX data set. We then relate the calibrated parameter values of these models to physical and climatological characteristics of the watershed using multivariate linear regression analysis, and evaluate the regionalization potential of our proposed models against those of the literature. If quality of fit is of main importance then the 3-parameter van Genuchten model is preferred, whereas the 2-parameter lognormal, 3-parameter GEV and generalized Pareto models show greater promise for regionalization.

The physical structure of a meteoroid may be inferred from optical observations, particularly the light curve, of a meteor. For example: a classically shaped (late peaked) light curve is seen as evidence of a solid single body, whereas a symmetric light curve may indicate a dustball structure. High-resolution optical observations show how the meteoroid fragments: continuously, leaving a long wake, or discretely, leaving several distinct pieces. Calculating the orbit of the meteoroid using two station data then allows the object to be associated with asteroidal or cometary parent bodies. Optical observations thus provide simultaneous information on meteoroid structure, fragmentation mode, and origin.CAMO (the Canadian Automated Meteor Observatory) has been continuously collecting faint (masses < 10-4 kg) two station optical meteors with image-intensified narrow field (with a resolution of up to 3 meters per pixel) and wide field (26 by 19 degrees) cameras since 2010. The narrow field, telescopic cameras allow the meteor fragmentation to be studied using a pair of mirrors to track the meteor. The wide-field cameras provide the light curve and trajectory solution.We present preliminary results from classifying light curves and high-resolution optical observations for 3000 faint meteors recorded since 2010. We find that most meteors (both asteroidal and cometary) show long trails, while meteors with short trails are the second most common morphology. It is expected that meteoroids that experience negligible fragmentation have the shortest trails, so our results imply that the majority of small meteoroids fragment during ablation. A surprising observation is that almost equal fractions of asteroidal and cometary meteors fragment (showing long trails), implying a similar structure for both types of meteoroids.

Contribution is focused on discussion of different design modifications of the volute, impeller and rotor-stator cavity in case of very low specific speed pump with recirculation channels. Amount of the liquid flowing through the recirculation channels has significant effect on delivery height, stability of the head curve and hydraulic efficiency. Analysis of these effects is based on the evaluation of the dissipated power in different internal parts of the pump and for different flow rates. It has already been proved in our previous research that volute has substantial impact on stability of the head curve. It is apparent that similar effect can also be attributed to distribution and shape of the recirculation channels. This fact is connected with the inflow into the channels and with magnitude of the flow rate through the recirculation channels. Influence of mentioned parameters on recirculation is discussed in present paper.

A three-dimensional running simulation program of the train motion which includes both electromagnetic and mechanical systems has been developed. For verification of running stability, the motion of the Maglev train with four bogies and three cars running into the curved section was calculated. Because the spring strength of the secondary suspension between bogies and cabins was much smaller than that of the electrodynamic suspension, interaction among bogies was small. The lateral displacement reached 0.045m, which is about 50% of the lateral air gap. Therefore train can run without touching the wall of the guideway. As this lateral air gap caused roll torque, total roll angle of the bogie became 12.5% larger than the cant angle of the curved section.

Electrospray Ionization (ESI) is a process whereby gas phase ions are created from molecules in solution. As a solution exits a narrow tube in the presence of a strong electric field, an aerosol of charged droplets are is formed that produces gas phase ions as they it desolvates. ESI-MS comprises the creation of ions by ESI and the determination of their mass to charge ratio (m/z) by MS.

The properties of thermoluminescence glow curves, containing one or more glow peaks, have been determined for situations where the assumptions invoked to obtain the usual first and second order kinetics do not apply. First order kinetics occurs only when retrapping is negligible. If more than one glow peak is present and retrapping occurs between different types of traps the glow peaks can be approximated, except in the wings, by the usual first and second order expressions; but often physically unrealistic parameters are obtained. These studies indicate that dating is best accomplished with minerals exhibiting first order kinetics. 6 figures, 1 table.

Runoff modeling is a key component in watershed management. The temporal course and amount of runoff is a complex function of a multitude of parameters such as climate, soil, topography, land use, and water management. Against the background of the current rapid environmental change, which is due to both i) man-made changes (e.g. urban development, land use change, water management) as well as ii) changes in the natural systems (e.g. climate change), understanding and predicting the impacts of these changes upon the runoff is very important and affects the wellbeing of many people living in the watershed. A main tool for predictions is hydrologic models. Particularly process based models are the method of choice to assess the impact of land use and climate change. However, many regions which experience large changes in the watersheds can be described as rather data poor, which limits the applicability of such models. This is particularly also true for the Telomoyo Watershed (545 km2) which is located in southern part of Central Java province. The average annual rainfall of the study area reaches 2971 mm. Irrigated paddy field are the dominating land use (35%), followed by built-up area and dry land agriculture. The only available soil map is the FAO soil digital map of the world, which provides rather general soil information. A field survey accompanied by a lab analysis 65 soil samples of was carried out to provide more detailed soil texture information. The soil texture map is a key input in the SCS method to define hydrological soil groups. In the frame of our study on 'Integrated Analysis on Flood Risk of Telomoyo Watershed in Response to the Climate and Land Use Change' funded by the German Academic Exchange service (DAAD) we analyzed the sensitivity of the modeled runoff upon the choice of the method to estimate the CN values using the SCS-CN method. The goal of this study is to analyze the impact of different data sources on the curve numbers and the

Nanotechnology based Pharma has emerged significantly and has influenced the Pharma industry up to a considerable extent. Nanoparticles technology holds a good share of the nanotech Pharma and is significant in comparison with the other domains. Electrospraying technology answers the potential needs of nanoparticle production such as scalability, reproducibility, effective encapsulation etc. Many drugs have been electrosprayed with and without polymer carriers. Drug release characteristics are improved with the incorporation of biodegradable polymer carriers which sustain the release of encapsulated drug. Electrospraying is acknowledged as an important technique for the preparation of nanoparticles with respect to pharmaceutical applications. Herein we attempted to consolidate the reports pertaining to electrospraying and their corresponding therapeutic application area. PMID:23512013

A relatively small number of satellites at high altitude orbits (20,000 km or higher) provide coverage of most of the Earth's surface. It is possible to have essentially continuous, day and night, all weather coverage over the entire surface of the Earth [1]. Space based infrared sensors have detected over 200 bright flashes in the atmosphere since 1972. Average number of flashes per year is 30. In addition optical sensors have detected 16 light curves in the visible (mainly during the last year). These bright flashes have been caused by explosive disintegration of large meteoroids in the atmosphere. Information from IR sensors and light curves have been analyzed. This analysis give important information on the energy - frequency distribution of the impacting meteoroids, their sizes, strengths and even composition. For an example, preatmospheric kinetic energies of meteoroids which caused 15 April 1988, 1 October 1990, 4 October 1991 and 1 February 1994 events are 8-9, 5-8, 1-2, and 40 kt TNT respectively. Three of them were stones or chondrites and deposited their energy at the altitudes of 30 to 45 km. Last one was probably an iron (initial velocity 24 km/sec, angle of trajectory inclination 45 degrees [2]) and penetrated to the altitude of about 20 km (strength of about 100 Mdyn/cm^2). Radiation-hydrodynamic 1D, 2D and even 3D numerical simulations [3,4] of the meteoroid flight in the atmosphere for various sizes, velocities, heights of flights have been conducted and used in the analysis. They were based on the detailed tables of spectral opacities for hot air and ablated material for various wavelengths, temperatures, densities, and composition (iron, stone, chondrite and cometary material). Radiation heat transfer, ablation, fragmentation, and dispersion of fragments have been taken into account. Detailed spectra of the emitted radiation has been obtained. Data from satellite network has been compared with the data from ground based photographic networks and

This study was conducted to determine the SWCC of unsaturated tropical residual soil in Kuala Lumpur, Malaysia. Undisturbed soil samples at five locations of high-risk slopes area were taken at a depth of 0.5 m using block sampler. In the determination of the SWCC, the pressure plate extractor with the capacity of 1500 kN/m2 has been used. The index properties of the soil such as natural moisture content, Atterberg limits, specific gravity, and soil classification are performed according to BS 1377: Part 2: 1990. The results of index properties show that the natural moisture content of the soil is between 36% to 46%, the plasticity index is between 10% - 26%, the specific gravity is between 2.51 - 2.61 and the soils is classified as silty organic clay of low plasticity. The SWCC data from the pressure plate extractor have been fitted with the Fredlund and Xing equation. The results show that the air entry value and residual matric suction for residual soils are in the range of 17 kN/m2 to 24 kN/m2 and 145 kN/m2 to 225 kN/m2 respectively. From the fitting curve, it is found that the average value of the Fredlund and Xing parameters such as a, n and m are in the range of 0.24-0.299, 1.7-4.8 and 0.142-0.440 respectively.

The hot deformation behavior of AISI 410 martensitic stainless steel was investigated by conducting hot compression tests between 1173 K (900 °C) and 1423 K (1150 °C) and between strain rates of 0.001 s-1 to 1 s-1. The hyperbolic sine function described the relation well between flow stress at a given strain and the Zener-Hollomon parameter ( Z). The variation of flow stress with deformation temperature gave the average value of apparent activation energy as 448 kJ/mol. The strain and stress corresponding to two important points associated with flow curve ( i.e., peak strain and the onset of steady-state flow) were related to the Z parameter using power-law equations. A model also was proposed based on the Johnson-Mehl-Avrami-Kolmogorov (JMAK) equation to estimate the fractional softening of dynamic recrystallization at any given strain. This model can be used readily for the prediction of flow stress. The values of n and k, material constants in the JMAK equation, were determined for the studied material. The strains regarding the peak and the onset of steady-state flow were formulated in term of applied strain rate and the constants of the JMAK equation. A good agreement was found between the predicted strains and those obtained by the experimental work.

The Curved Duct Test Rig (CDTR), which is designed to investigate propagation of sound in a duct with flow, has been developed at NASA Langley Research Center. The duct incorporates an adaptive control system to generate a tone in the duct at a specific frequency with a target Sound Pressure Level and a target mode shape. The size of the duct, the ability to isolate higher order modes, and the ability to modify the duct configuration make this rig unique among experimental duct acoustics facilities. An experiment is described in which the facility performance is evaluated by measuring the sound attenuation by a sample duct liner. The liner sample comprises one wall of the liner test section. Sound in tones from 500 to 2400 Hz, with modes that are parallel to the liner surface of order 0 to 5, and that are normal to the liner surface of order 0 to 2, can be generated incident on the liner test section. Tests are performed in which sound is generated without axial flow in the duct and with flow at a Mach number of 0.275. The attenuation of the liner is determined by comparing the sound power in a hard wall section downstream of the liner test section to the sound power in a hard wall section upstream of the liner test section. These experimentally determined attenuations are compared to numerically determined attenuations calculated by means of a finite element analysis code. The code incorporates liner impedance values educed from measured data from the NASA Langley Grazing Incidence Tube, a test rig that is used for investigating liner performance with flow and with (0,0) mode incident grazing. The analytical and experimental results compare favorably, indicating the validity of the finite element method and demonstrating that finite element prediction tools can be used together with experiment to characterize the liner attenuation.

The major potential errors in the slit method measurement of the line spread function (LSF) and the modu-lation transfer function (MTF) of radiographic screen-film systems are reviewed. These errors are compared with the potential error introduced in the LSF due to an erroneous representation of the characteristiccurve (sensitometric data). If a deviation in the sensitometric data results in a lower average gradient of the characteristiccurve, the MTF will show higher resolution capabilities.

Streams in the Appalachian Plateaus Physiographic Province in West Virginia were classified as a single region on the basis of bankfull characteristics. Regression lines for annual peak flow and drainage area measured at streamgages in the study area at recurrence intervals between 1.2 and 1.7 years fell within the 99-percent confidence interval of the regression line for bankfull flow. Channel characteristics were intermediate among those from surrounding states and regions where comparable studies have been done. The stream reaches that were surveyed were selected for apparent stability, and to represent gradients of drainage area, elevation, and mean annual precipitation. Profiles of high-water marks left by bankfull and near-bankfull peaks were surveyed, either as part of slope-area flow measurements at ungaged reaches, or to transfer known flow information to cross sections for gaged reaches. The slope-area measurements made it possible to include ungaged sites in the study, but still relate bankfull dimensions to peak flow and frequency.

Using receiver-operating characteristic (ROC) curve methodology this study was designed to assess the diagnostic effectiveness of somatic cell count (SCC) and the California mastitis test (CMT) in Valle del Belice sheep, and to propose and evaluate threshold values for those tests that would optimally discriminate between healthy and infected udders. Milk samples (n=1357) were collected from 684 sheep in four flocks. The prevalence of infection, as determined by positive bacterial culture was 0.36, 87.7% of which were minor and 12.3% major pathogens. Of the culture negative samples, 83.7% had an SCC<500,000/mL and 97.4% had <1,000,000cells/mL. When the associations between SC score (SCS) and whole sample status (culture negative vs. infected), minor pathogen status (culture negative vs. infected with minor pathogens), major pathogen status (culture negative vs. infected with major pathogens), and CMT results were evaluated, the estimated area under the ROC curve was greater for glands infected with major compared to minor pathogens (0.88 vs. 0.73), whereas the area under the curve considering all pathogens was similar to the one for minor pathogens (0.75). The estimated optimal thresholds were 3.00 (CMT), 2.81 (SCS for the whole sample), 2.81 (SCS for minor pathogens), and 3.33 (SCS for major pathogens). These correctly classified, respectively, 69.0%, 73.5%, 72.6% and 91.0% of infected udders in the samples. The CMT appeared only to discriminate udders infected with major pathogens. In this population, SCS appeared to be the best indirect test of the bacteriological status of the udder. PMID:23317658

Curved twin I-girder bridges (CTIGBs) have low torsional stiffness that makes them vulnerable to dynamic loads. This study investigates the effects of bottom bracings on the torsional dynamic characteristics of CTIGBs. Five types of bottom bracings are designed to investigate their effects on the dynamic characteristics of CTIGBs with different curvatures under free and forced vibrations. To perform numerical investigations, three-dimensional (3-D) finite element (FE) bridge and vehicle models are established using commercial ANSYS code, and then a vehicle-bridge interaction analysis approach is proposed. Road roughness profiles generated from power spectral density and cross spectral functions are also taken into account in the analyses. The numerical results show that torsional frequencies increase significantly after providing bottom bracings, and the increasing rate depends on the type of bottom bracings and their locations of installation. Bottom bracings can act as load transmitting members from one main girder to the others. Large negative bearing forces that have occurred in bridges with small radii of curvatures can be remarkably reduced by providing bottom bracing systems. It is found that the performances of several bottom bracing systems are effective in improving the torsional dynamic characteristics of the bridges in this study.

Therapeutic drug monitoring studies of selective serotonin reuptake inhibitor (SSRI) antidepressants thus far failed to identify a clear concentration-response relationship in major depression. Majority of the previous studies defined clinical response as 50% or greater reduction from baseline in depression rating scale scores. Because many patients who meet these criteria still present symptoms associated with functional impairment, there is a need to consider "remission" as an alternative end point in concentration-response analyses of SSRIs. The present 12-week prospective study investigated the relationship between fluvoxamine (an SSRI) plasma concentration and remission in outpatients with depression. We used a flexible dose titration study designed to mimic clinical practice within the therapeutic dose range of fluvoxamine (25-200 mg/d). Receiver operating characteristics (ROC) curve was computed to determine the optimal fluvoxamine plasma concentration for remission using 269 concentration data obtained from 80 patients. Analysis of the ROC curve from the entire study sample did not reveal a fluvoxamine concentration significantly predicting remission. By contrast, ROC analysis specifically in patients with moderate to severe depression (N = 51; baseline 17-item Hamilton Rating Scale for Depression score > or = 20) found a fluvoxamine concentration of 61.4 ng/mL as a significant predictor of remission. In conclusion, therapeutic drug monitoring may be useful for rational titration and individualization of fluvoxamine dose and predicting remission in patients with moderate to severe depression, who may presumably display lesser placebo component in pharmacodynamic response. PMID:18480690

The flow rate at the terminal spring of a 1929 ha karst ground-water catchment has been continuously monitored for 2 years, and 108 identifiable events were analyzed. The peak flow rates followed a beta frequency distribution with parameters ?? = 0.365 and ?? = 1.135. Events were separated into high-flow and low-flow. High-flow events had characteristics attributable to pipe flow. Correlation and stepwise regression were used to develop peak flow rate prediction equations for the combined 108 events and for the 81 low-flow events. The portion of the recession curve identified as pipe flow was a watershed constant and time invariant. The base flow was seasonal, increasing in the winter to approximately 0.071 m3s-1 and decreasing in the summer to approximately 0.014 m3s-1. ?? 1994.

During recent years, nanoscaled materials have gained much attention because of their applications in the field of pharmaceutical and biomedical sciences. Electrospinning/electrospraying, as simple, effective and single-step methods, are used in the preparation of nanostructured materials (nanofibers and nanobeads). They offer an opportunity for direct encapsulation of the different types of drug molecules. The generated nanomaterials possess high surface area with porous characteristics, and the liberation of the loaded drugs follows a controlled-release pattern. Because of their wide applications in medical/pharmaceutical researches, the aim of this editorial is to highlight the importance of electrospinning/electrospraying technologies in drug delivery. PMID:27340617

Based on fractal theory, the fractal characteristics of soil particle size distribution (PSD) and soil water retention curve (WRC) under the five vegetation types were studied in the mountainous land of Northern China. Results showed that: (1) the fractal parameters of soil PSD and soil WRC varied greatly under each different vegetation type, with Quercus acutissima Carr. and Robina pseudoacacia Linn. mixed plantation (QRM) > Pinus thunbergii Parl. and Pistacia chinensis Bunge mixed plantation (PPM) > Pinus thunbergii Parl. (PTP) > Juglans rigia Linn. (JRL) > abandoned grassland (ABG); (2) the soil fractal dimensions of woodlands (QRM, PPM, PTP and JRL) were significantly higher than that in ABG, and mixed forests (QRM and PPM) were higher than that in pure forests (PTP and JRL); (3) the fractal dimension of soil was positively correlated with the silt and clay content but negatively correlated with the sand content; and (4) the fractal dimension of soil PSD was positively correlated with the soil WRC. These indicated that the fractal parameters of soil PSD and soil WRC could act as quantitative indices to reflect the physical properties of the soil, and could be used to describe the influences of the Return Farmland to Forests Projects on soil structure. PMID:26633458

Based on fractal theory, the fractal characteristics of soil particle size distribution (PSD) and soil water retention curve (WRC) under the five vegetation types were studied in the mountainous land of Northern China. Results showed that: (1) the fractal parameters of soil PSD and soil WRC varied greatly under each different vegetation type, with Quercus acutissima Carr. and Robina pseudoacacia Linn. mixed plantation (QRM) > Pinus thunbergii Parl. and Pistacia chinensis Bunge mixed plantation (PPM) > Pinus thunbergii Parl. (PTP) > Juglans rigia Linn. (JRL) > abandoned grassland (ABG); (2) the soil fractal dimensions of woodlands (QRM, PPM, PTP and JRL) were significantly higher than that in ABG, and mixed forests (QRM and PPM) were higher than that in pure forests (PTP and JRL); (3) the fractal dimension of soil was positively correlated with the silt and clay content but negatively correlated with the sand content; and (4) the fractal dimension of soil PSD was positively correlated with the soil WRC. These indicated that the fractal parameters of soil PSD and soil WRC could act as quantitative indices to reflect the physical properties of the soil, and could be used to describe the influences of the Return Farmland to Forests Projects on soil structure. PMID:26633458

The concentration addition (CA) model has been widely applied to predict mixture toxicity. However, its applicability is difficult to evaluate due to the complexity of interactions among substances. Considering that the concentration-response curve (CRC) of each component of the mixture is closely related to the prediction of mixture toxicity, mathematical treatments were used to derive a characteristic index kECx (k was the slope of the tangent line of a CRC at concentration ECx). The implication is that the CA model would be applicable for predicting the mixture toxicity only when chemical components have similar kECx in the whole or part of the concentration range. For five selected chemicals whose toxicity was detected using luminescent bacteria, sodium dodecyl benzene sulfonate (SDBS) showed much higher kECx values than the others and its existence in the binary mixtures brought about overestimation of the mixture toxicity with the CA model. The higher the mass ratio of SDBS in a multi-mixture was, the more the toxicity prediction deviated from measurements. By applying the method proposed in this study to analyze some published data, it is confirmed that some components having significantly different kECx values from the other components could explain the large deviation of the mixture toxicity predicted by the CA model. PMID:25499050

Electrospray is a technique that uses large electric fields to generate a spray of highly-charged, monodispersed droplets from a liquid solvent. Colloidal inks, consisting of nanoparticles dispersed in a volatile solvent, can be atomized using electrospray. In this study, we investigate the deposit structure of nanoparticle inks printed onto three different substrates: bare glass, silanized-patterned glass, and glass coated with a liquid film. The deposition morphology of colloidal inks printed onto these surfaces is predicted using mathematical modeling and statistical analysis. The goal of intervening at the substrate with surface patterns and liquid films is to exert control over the microstructure of the printed deposit. The advantage of electrospray is that it is an additive process which drastically reduces material waste that is inherent in other thin-film material processes.

Receiver operating characteristic (ROC) curves were generated to obtain classification area under the curve (AUC) as a function of feature standardization, fuzzification, and sample size from nine large sets of cancer-related DNA microarrays. Classifiers used included k nearest neighbor (kNN), näive Bayes classifier (NBC), linear discriminant analysis (LDA), quadratic discriminant analysis (QDA), learning vector quantization (LVQ1), logistic regression (LOG), polytomous logistic regression (PLOG), artificial neural networks (ANN), particle swarm optimization (PSO), constricted particle swarm optimization (CPSO), kernel regression (RBF), radial basis function networks (RBFN), gradient descent support vector machines (SVMGD), and least squares support vector machines (SVMLS). For each data set, AUC was determined for a number of combinations of sample size, total sum[−log(p)] of feature t-tests, with and without feature standardization and with (fuzzy) and without (crisp) fuzzification of features. Altogether, a total of 2,123,530 classification runs were made. At the greatest level of sample size, ANN resulted in a fitted AUC of 90%, while PSO resulted in the lowest fitted AUC of 72.1%. AUC values derived from 4NN were the most dependent on sample size, while PSO was the least. ANN depended the most on total statistical significance of features used based on sum[−log(p)], whereas PSO was the least dependent. Standardization of features increased AUC by 8.1% for PSO and -0.2% for QDA, while fuzzification increased AUC by 9.4% for PSO and reduced AUC by 3.8% for QDA. AUC determination in planned microarray experiments without standardization and fuzzification of features will benefit the most if CPSO is used for lower levels of feature significance (i.e., sum[−log(p)] ~ 50) and ANN is used for greater levels of significance (i.e., sum[−log(p)] ~ 500). When only standardization of features is performed, studies are likely to benefit most by using CPSO for low

Blossom blight forecasting is an important aspect of fire blight, caused by Erwinia amylovora, management for both apple and pear. A comparison of the forecast accuracy of two common fire blight forecasters, MARYBLYT and Cougarblight, was performed with receiver operating characteristic (ROC) curve...

Developed an item characteristiccurve estimation of signal detection theory based personality data. Results for 266 college students taking the Overclaiming Questionnaire (D. Paulhus and N. Bruce, 1990) suggest that this method is a reasonable approach to describing item functioning and that there are advantages to this method over traditional…

A report describes ElectroSpray Ionization based Electrostatic Precipitation (ESIEP) for collecting lunar dust particles. While some HEPA filtration processes may remove a higher fraction (>99.9 percent) of the particles, the high efficiency may not be appropriate from an overall system standpoint, especially in light of the relatively large power requirement that such systems demand. The new electrospray particle capture technology is described as a variant of electrostatic precipitation that eliminates the current drawbacks of electrostatic precipitation. The new approach replaces corona prone field with a mist of highly charged micro-droplets generated by electrospray ionization (ESI) as the mechanism by which incoming particles are attracted and captured. In electrospray, a miniscule flow rate (microliters/minute) of liquid (typically water and a small amount of salt to enhance conductivity) is fed from the tip of a needle held at a high voltage potential relative to an opposite counter electrode. At sufficient field strength, a sharp liquid meniscus forms , which emits a jet of highly charged droplets that drift through the surrounding gas and are collected on the walls of a conductive tube. Particles in the gas have a high probability of contact with the droplets either by adhering to the droplets or otherwise acquiring a high level of charge, causing them to be captured on the collecting electrode as well. The spray acts as a filtration material that is continuously introduced and removed from the gas flow, and thus can never become clogged.

Drops subjected to strong electric fields emit thin fluid jets from conical structures (Taylor cones) that form at their surfaces. Such behavior has practical, e.g. electrospray mass spectrometry, and fundamental, e.g. raindrops in thunderclouds, implications. Theoretical analysis of the temporal development of such EHD tip-streaming phenomena is challenging given the large disparity in length scales between the macroscopic drops and the microscopic jets. Furthermore, there exist conflicting theories and measurements on the size and charge of these small electrospray droplets. We use theory and simulation to show that conductivity can be tuned to yield three scaling regimes for droplet radius and charge, a finding missed by previous studies. The amount of charge Q that electrospray droplets carry determines whether they are coulombically stable and charged below the Rayleigh limit of stability R or are unstable and hence prone to further explosions once formed. Previous experiments reported droplet charge values ranging from 1/10th to in excess of R. Simulations unequivocally show that electrospray droplets are coulombically stable at the instant they are created and that there exists a universal scaling law for droplet charge, Q=0.44 R.

Suppression of ion intensity in the presence of high salt matrices is common in most mass spectrometry ionization techniques. Desorption electrospray ionization (DESI) is an ionization method that exhibits salt tolerance, and this is investigated. DESI analysis was performed on three different drug mixtures in the presence of 0, 0.2, 2, 5, 10, and 20% NaCl:KCl weight by volume from seven different surfaces. At physiological concentrations individual drugs in each mixture were observed with each surface. Collision-induced dissociation (CID) was used to provide additional confirmation for select compounds. Multiple stage experiments, to MS5, were performed for select compounds. Even in the absence of added salt, the benzodiazepine containing mixture yielded sodium and potassium adducts of carbamazepine which masked the ions of interest. These adducts were eliminated by adding 0.1% 7M ammonium acetate to the standard methanol:water (1:1) spray solvent. Comparison of the salt tolerance of DESI with that of electrospray ionization (ESI) demonstrated much better signal/noise characteristics for DESI in this study. The salt tolerance of DESI was also studied by performing limit of detection and dynamic range experiments. Even at a salt concentration significantly above physiological concentrations, select surfaces were effective in providing spectra that allowed the ready identification of the compounds of interest. The already high salt tolerance of DESI can be optimized further by appropriate choices of surface and spray solution.

Electrospray ionization emitter arrays, as well as methods for forming electrosprays, are described. The arrays are characterized by a radial configuration of three or more nano-electrospray ionization emitters without an extractor electrode. The methods are characterized by distributing fluid flow of the liquid sample among three or more nano-electrospray ionization emitters, forming an electrospray at outlets of the emitters without utilizing an extractor electrode, and directing the electrosprays into an entrance to a mass spectrometry device. Each of the nano-electrospray ionization emitters can have a discrete channel for fluid flow. The nano-electrospray ionization emitters are circularly arranged such that each is shielded substantially equally from an electrospray-inducing electric field.

... sampling plan for normal condition of container inspection from Table I or Table I-A of § 42.109. (b) For a... sampling plan of size 168 for normal inspection (Table I of § 42.109) along with an AQL for total defects of 6.5. The OC curve for this sampling plan is curve N and R3. Also, assume that the quality of...

... sampling plan for normal condition of container inspection from Table I or Table I-A of § 42.109. (b) For a... sampling plan of size 168 for normal inspection (Table I of § 42.109) along with an AQL for total defects of 6.5. The OC curve for this sampling plan is curve N and R3. Also, assume that the quality of...

... sampling plan for normal condition of container inspection from Table I or Table I-A of § 42.109. (b) For a... sampling plan of size 168 for normal inspection (Table I of § 42.109) along with an AQL for total defects of 6.5. The OC curve for this sampling plan is curve N and R3. Also, assume that the quality of...

... sampling plan for normal condition of container inspection from Table I or Table I-A of § 42.109. (b) For a... sampling plan of size 168 for normal inspection (Table I of § 42.109) along with an AQL for total defects of 6.5. The OC curve for this sampling plan is curve N and R3. Also, assume that the quality of...

... sampling plan for normal condition of container inspection from Table I or Table I-A of § 42.109. (b) For a... sampling plan of size 168 for normal inspection (Table I of § 42.109) along with an AQL for total defects of 6.5. The OC curve for this sampling plan is curve N and R3. Also, assume that the quality of...

Optical observations of faint meteors (10-7 < mass < 10-4 kg) were collected by the Canadian Automated Meteor Observatory between 2010 April and 2014 May. These high-resolution (metre scale) observations were combined with two-station light-curve observations and the meteoroid orbit to classify meteors and attempt to answer questions related to meteoroid fragmentation, strength, and light-curve shape. The F parameter was used to classify the meteor light-curve shape; the observed morphology was used to classify the fragmentation mode; and the Tisserand parameter described the origin of the meteoroid. We find that most meteor light curves are symmetric (mean F parameter 0.49), show long distinct trails (continuous fragmentation), and are cometary in origin. Meteors that show no obvious fragmentation (presumably single body objects) show mostly symmetric light curves, surprisingly, and this indicates that light-curve shape is not an indication of fragility or fragmentation behaviour. Approximately 90 per cent of meteors observed with high-resolution video cameras show some form of fragmentation. Our results also show, unexpectedly, that meteors which show negligible fragmentation are more often on high-inclination orbits (i > 60°) than low-inclination ones. We also find that dynamically asteroidal meteors fragment as often as dynamically cometary meteors, which may suggest mixing in the early Solar system, or contamination between the dynamic groups.

Regional hydraulic geometry curves are power-function equations that relate riffle dimensions and bankfull discharge to drainage-basin size. They are defined by data collected through surveys conducted at stable stream reaches and can be used to aid watershed managers, design engineers, and others involved in determination of the best course of action for an unstable stream. Hydraulic geometry curves provide a mechanism through which comparisons can be made between riffle dimensions collected at an unstable stream to those collected at stable streams within the same region. In 2005, a study was initiated to delineate regional hydraulic geometry curves for Michigan. After in-office review of 343 U.S. Geological Survey streamgaging stations and an extensive field reconnaissance effort, 44 stable reaches were selected for this study. Detailed surveys that included cross-sectional and longitudinal profiles and pebble counts were conducted at selected streamgages, which were distributed throughout Michigan. By use of survey data from riffle cross sections and water-surface slope, bankfull discharge was estimated and compared to flood-recurrence intervals using regional flood equations. This comparison shows that bankfull discharges in Michigan recur more frequently than every 2 years. Regional hydraulic geometry curves were developed rather than statewide curves owing to large differences in factors that control channel geometry across the State. However, after the data were subdivided according to ecoregions, it was determined that there were enough data to delineate regional hydraulic geometry curves only for the Southern Lower Michigan Ecoregion. For this ecoregion, geometry curve equations and their coefficients of determination are: Width = 8.19 x DA0.44; R2 = 0.69, Depth = 0.67 x DA0.27; R2 = 0.28, Area = 4.38 x DA0.74; R2 = 0.59, where DA is the drainage area and R2 is the coefficient of determination. By use of discharge estimates for the Southern Lower Michigan

Many novel functional structures are now fabricated by controlled deposition as a maskless, bottom-up fabrication technique. These applications require rapid and precise deposition of minute amounts of solutions/suspensions or their ultimate particle products in predefined patterns. The electrospray is a promising alternative to the commonly used inkjet printing because it can easily handle highly viscous liquid, avoid high shear rates, and has low risk of clogging. We demonstrate a proof-of-concept digital electrospray. This system consists of a 61-nozzle array microfabricated in silicon and a 61-element digital extractor fabricated using flexible polyimide substrates. "Digital" refers to the state of each electrospray source that can be tuned either on or off independently and responsively. We showed a resolution of 675 mum and a response frequency up to 100 Hz. With similar design and industry standard fabrication procedures, it is feasible to scale up the system to O(1000) sources with spatial resolution better than 250 mum and a O(kHz) response frequency. The latter is controlled by the viscous damping time. PMID:20370220

As miniaturization of electrospray continues to become more prevalent in the mass spectrometry arsenal, numerous types of conductive coatings have been developed with miniaturized electrospray emitters. Different conductive coatings have different properties that may lead to differences in analytical performance. This paper investigates and compares the analytical properties of a series of applied conductive coatings for low-flow electrospray ionization developed in this laboratory vs. commercially-available types. Evaporated graphite is thoroughly compared with commercially available polyaniline (PANI) coated emitters and metal coated emitters. Each set of emitters was investigated to determine various performance characteristics, including susceptibility to electrical discharge in both positive and negative ionization modes, as well as emitter reproducibility and generation of a standard curve to determine each emitter coating's limit of detection and limit of quantitation. Furthermore, evaporated graphite and polyaniline coated fused silica capillaries were investigated to determine which coating is more stable over long-term analyses and during electrical discharge. PMID:16568172

Purpose: From independently conducted free-response receiver operating characteristic (FROC) and receiver operating characteristic (ROC) experiments, to study fixed-reader associations between three estimators: the area under the alternative FROC (AFROC) curve computed from FROC data, the area under the ROC curve computed from FROC highest rating data, and the area under the ROC curve computed from confidence-of-disease ratings. Methods: Two hundred mammograms, 100 of which were abnormal, were processed by two image-processing algorithms and interpreted by four radiologists under the FROC paradigm. From the FROC data, inferred-ROC data were derived, using the highest rating assumption. Eighteen months afterwards, the images were interpreted by the same radiologists under the conventional ROC paradigm; conventional-ROC data (in contrast to inferred-ROC data) were obtained. FROC and ROC (inferred, conventional) data were analyzed using the nonparametric area-under-the-curve (AUC), (AFROC and ROC curve, respectively). Pearson correlation was used to quantify the degree of association between the modality-specific AUC indices and standard errors were computed using the bootstrap-after-bootstrap method. The magnitude of the correlations was assessed by comparison with computed Obuchowski-Rockette fixed reader correlations. Results: Average Pearson correlations (with 95% confidence intervals in square brackets) were: Corr(FROC, inferred ROC) = 0.76[0.64, 0.84] > Corr(inferred ROC, conventional ROC) = 0.40[0.18, 0.58] > Corr (FROC, conventional ROC) = 0.32[0.16, 0.46]. Conclusions: Correlation between FROC and inferred-ROC data AUC estimates was high. Correlation between inferred- and conventional-ROC AUC was similar to the correlation between two modalities for a single reader using one estimation method, suggesting that the highest rating assumption might be questionable. PMID:23039631

Purpose: From independently conducted free-response receiver operating characteristic (FROC) and receiver operating characteristic (ROC) experiments, to study fixed-reader associations between three estimators: the area under the alternative FROC (AFROC) curve computed from FROC data, the area under the ROC curve computed from FROC highest rating data, and the area under the ROC curve computed from confidence-of-disease ratings. Methods: Two hundred mammograms, 100 of which were abnormal, were processed by two image-processing algorithms and interpreted by four radiologists under the FROC paradigm. From the FROC data, inferred-ROC data were derived, using the highest rating assumption. Eighteen months afterwards, the images were interpreted by the same radiologists under the conventional ROC paradigm; conventional-ROC data (in contrast to inferred-ROC data) were obtained. FROC and ROC (inferred, conventional) data were analyzed using the nonparametric area-under-the-curve (AUC), (AFROC and ROC curve, respectively). Pearson correlation was used to quantify the degree of association between the modality-specific AUC indices and standard errors were computed using the bootstrap-after-bootstrap method. The magnitude of the correlations was assessed by comparison with computed Obuchowski-Rockette fixed reader correlations. Results: Average Pearson correlations (with 95% confidence intervals in square brackets) were: Corr(FROC, inferred ROC) = 0.76[0.64, 0.84] > Corr(inferred ROC, conventional ROC) = 0.40[0.18, 0.58] > Corr (FROC, conventional ROC) = 0.32[0.16, 0.46]. Conclusions: Correlation between FROC and inferred-ROC data AUC estimates was high. Correlation between inferred- and conventional-ROC AUC was similar to the correlation between two modalities for a single reader using one estimation method, suggesting that the highest rating assumption might be questionable.

This manual describes graphical and mathematical procedures for preparing frequency curves from samples of hydrologic data. It also discusses the theory of frequency curves, compares advantages of graphical and mathematical fitting, suggests methods of describing graphically defined frequency curves analytically, and emphasizes the correct interpretations of a frequency curve.

The dependence of the shape of the glow curve of LiF:Mg,Ti (TLD-100) on ionisation density was investigated using irradiation with 90Sr/90Y beta rays, 60 and 250 kVp X rays, various heavy-charged particles and 0.2 and 14 MeV neutrons. Special attention is focused on the properties of high-temperature thermoluminescence; specifically, the behaviour of the high-temperature ratio (HTR) of Peaks 7 and 8 as a function of batch and annealing protocol. The correlation of Peaks 7 and 8 with average linear-energy-transfer (LET) is also investigated. The HTR of Peak 7 is found to be independent of LET for values of LET approximately >30 keV µm−1. The behaviour of the HTR of Peak 8 with LET is observed to be erratic, which suggests that applications using the HTR should separate the contributions of Peaks 7 and 8 using computerised glow curve deconvolution. The behaviour of the HTR following neutron irradiation is complex and not fully understood. The shape of composite Peak 5 is observed to be broader following high ionisation alpha particle irradiation, suggesting that the combined use of the HTR and the shape of Peak 5 could lead to improved ionisation density discrimination for particles of high LET. PMID:18667402

Electrospraying is an innovative method to deposit very small amounts of, for example, biofluids (far less than 1 p1) that include DNA or protein molecules. An electric potential is applied between a nozzle filled with liquid and a counter electrode placed at 1-2 millimeter distance from the nozzle. In our set-up we use an AC field superposed on a DC field to control the droplet generation process. Our approach is to create single events of electrospraying triggered by one single AC pulse. During this pulse, the equilibrium meniscus (determined by surface tension, static pressure and the DC field) of the liquid changes rapidly into a cone and subsequently into a jet formed at the cone apex. Next, the jet breaks-up into fine droplets and the spraying stops. The meniscus returns to its equilibrium shape again. So far we obtained a stable and reproducible single event process for ethanol and ethylene glycol with water using glass pipettes. The results will be used to generate droplets on demand in a controlled way and deposit them on a pre-defined place on the substrate.

Objective To assess the cutoff values established by ROC curves to classify 18F-NaF uptake as normal or malignant. Materials and Methods PET/CT images were acquired 1 hour after administration of 185 MBq of 18F-NaF. Volumes of interest (VOIs) were drawn on three regions of the skeleton as follows: proximal right humerus diaphysis (HD), proximal right femoral diaphysis (FD) and first vertebral body (VB1), in a total of 254 patients, totalling 762 VOIs. The uptake in the VOIs was classified as normal or malignant on the basis of the radiopharmaceutical distribution pattern and of the CT images. A total of 675 volumes were classified as normal and 52 were classified as malignant. Thirty-five VOIs classified as indeterminate or nonmalignant lesions were excluded from analysis. The standardized uptake value (SUV) measured on the VOIs were plotted on an ROC curve for each one of the three regions. The area under the ROC (AUC) as well as the best cutoff SUVs to classify the VOIs were calculated. The best cutoff values were established as the ones with higher result of the sum of sensitivity and specificity. Results The AUCs were 0.933, 0.889 and 0.975 for UD, FD and VB1, respectively. The best SUV cutoffs were 9.0 (sensitivity: 73%; specificity: 99%), 8.4 (sensitivity: 79%; specificity: 94%) and 21.0 (sensitivity: 93%; specificity: 95%) for UD, FD and VB1, respectively. Conclusion The best cutoff value varies according to bone region of analysis and it is not possible to establish one value for the whole body. PMID:26929455

It is good scientific practice to the report an appropriate estimate of effect size and a confidence interval (CI) to indicate the precision with which a population effect was estimated. For comparisons of 2 independent groups, a probability-based effect size estimator (A) that is equal to the area under a receiver operating characteristic curve…

The area under the time-dependent ROC curve (AUC) may be used to quantify the ability of a marker to predict the onset of a clinical outcome in the future. For survival analysis with competing risks, two alternative definitions of the specificity may be proposed depending of the way to deal with subjects who undergo the competing events. In this work, we propose nonparametric inverse probability of censoring weighting estimators of the AUC corresponding to these two definitions, and we study their asymptotic properties. We derive confidence intervals and test statistics for the equality of the AUCs obtained with two markers measured on the same subjects. A simulation study is performed to investigate the finite sample behaviour of the test and the confidence intervals. The method is applied to the French cohort PAQUID to compare the abilities of two psychometric tests to predict dementia onset in the elderly accounting for death without dementia competing risk. The 'timeROC' R package is provided to make the methodology easily usable. PMID:24027076

Our goal is to develop a probabilistic sonar performance prediction methodology that can make use of limited knowledge of random or uncertain environment, target, and sonar system parameters, but does not make unwarranted assumptions. The maximum entropy method (MEM) can be used to construct probability density functions (pdfs) for relevant environmental and source parameters, and an ocean acoustic propagation model can use those pdfs to predict the variability of received signal parameter. At this point, the MEM can be used once again to produce signal parameter pdfs. A Bayesian framework allows these pdfs to be incorporated into the signal processor to produce ROC curves in which, for example, the signal-to-noise ratio (SNR) is a random variable for which a pdf has been calculated. One output of such a processor could be a range-dependent probability of detection for fixed probability of false alarm, which would be more useful than the conventional range of the day that is still in use in some areas. [Work supported by ONR Code 321US.

A new type of cluster SIMS, named as electrospray droplet impact (EDI), has been developed in our laboratory. It was found that peptides deposited on the stainless steel substrate were ionized/desorbed without the accumulation of radiation products. The organic samples with film thickness thinner than 10 monolayers are desorbed/ionized with little damage underneath the surface. In general, rather strong negative ions as well as positive ions are generated. The mechanism for the ionization/desorption in EDI is much less complicated than those for MALDI and SIMS due to the fact that only very thin sample layers take part in the shock-wave excited selvedge and higher-order side reactions are largely suppressed.

An electrospray device includes a high voltage electrode chamber. The high voltage electrode chamber includes an inlet for receiving a fluid to be ionized and for directing the fluid into the chamber and at least one electrode having an exposed surface within the chamber. A flow channel directs fluid over a surface of the electrode and out of the chamber. The length of the flow channel over the electrode is greater than the height of the flow channel over the electrode, thereby producing enhanced mass transport to the working electrode resulting in improved electrolysis efficiency. An outlet is provided for transmitting the fluid out from the electrode chamber. A method of creating charged droplets includes flowing a fluid over an electrode where the length over the electrode is greater than the height of the fluid flowing over the electrode.

Development of electrospray ionization on solid substrates (solid-substrate ESI) avoids the clogging problem encountered in conventional capillary-based ESI, allows more convenient sampling and permits new applications. So far, solid-substrate ESI with various materials, e.g., metals, paper, wood, fibers and biological tissue, has been developed, and applications ranging from analysis of pure compounds to complex mixtures as well as in vivo study were demonstrated. Particularly, the capability of solid-substrate ESI in direct analysis of complex samples, e.g., biological fluids and foods, has significantly facilitated mass spectrometric analysis in real-life applications and led to increasingly important roles of these techniques nowadays. In this review, various solid-substrate ESI techniques and their applications are summarized and the prospects in this field are discussed. PMID:26819900

A commercial air ejector was coupled to an electrospray ionization linear ion trap mass spectrometer (LTQ) to transport remotely generated ions from both electrospray (ESI) and desorption electrospray ionization (DESI) sources. We demonstrate the remote analysis of a series of analyte ions that range from small molecules and polymers to polypeptides using the AE-LTQ interface. The details of the ESI-AE-LTQ and DESI-AE-LTQ experimental configurations are described and preliminary mass spectrometric data are presented. PMID:17716909

A commercial air ejector was coupled to an electrospray ionization linear ion trap mass spectrometer (LTQ) to transport remotely generated ions from both electrospray (ESI) and desorption electrospray ionization (DESI) sources. We demonstrate the remote analysis of a series of analyte ions that range from small molecules and polymers to polypeptides using the AE-LTQ interface. The details of the ESI-AE-LTQ and DESI-AE-LTQ experimental configurations are described and preliminary mass spectrometric data is presented. PMID:17716909

An electrospray ion (ESI) source and method capable of ionizing an analyte molecule without oxidizing or reducing the analyte of interest. The ESI source can include an emitter having a liquid conduit, a working electrode having a liquid contacting surface, a spray tip, a secondary working electrode, and a charge storage coating covering partially or fully the liquid contacting surface of the working electrode. The liquid conduit, the working electrode and the secondary working electrode can be in liquid communication. The electrospray ion source can also include a counter electrode proximate to, but separated from, said spray tip. The electrospray ion source can also include a power system for applying a voltage difference between the working electrodes and a counter-electrode. The power system can deliver pulsed voltage changes to the working electrodes during operation of said electrospray ion source to minimize the surface potential of the charge storage coating.

An electrospray ion (ESI) source and method capable of ionizing an analyte molecule without oxidizing or reducing the analyte of interest. The ESI source can include an emitter having a liquid conduit, a working electrode having a liquid contacting surface, a spray tip, a secondary working electrode, and a charge storage coating covering partially or fully the liquid contacting surface of the working electrode. The liquid conduit, the working electrode and the secondary working electrode can be in liquid communication. The electrospray ion source can also include a counter electrode proximate to, but separated from, said spray tip. The electrospray ion source can also include a power system for applying a voltage difference between the working electrodes and a counter-electrode. The power system can deliver pulsed voltage changes to the working electrodes during operation of said electrospray ion source to minimize the surface potential of the charge storage coating.

In this study, we report a simple and economical ballpoint electrospray ionization mass spectrometry (BP-ESI-MS) technique. This combines a small ballpoint tip with a syringe pump for the direct loading and ionization of various samples in different phases (including solution, semisolid, and solid) and allows for additional applications in surface analysis. The tiny metal ball on the ballpoint tip exhibits a larger surface for ionization than that of a conventional sharp tip end, resulting in higher ionization efficiency and less sample consumption. The adamant properties of the ballpoint tip allow sampling by simply penetrating or scraping various surfaces, such as a fruit peel, paper, or fabric. Complex samples, such as fine herbal powders and small solid samples, could be stored in the hollow space in the ballpoint socket and subsequently extracted online, which greatly facilitated MS analysis with little to no sample preparation. Positive ion mode was attempted, and various compounds, including amino acids, carbohydrates, flavonoids, and alkaloids, were detected from different types of samples. The results demonstrated that the special and excellent physical characteristics of ballpoint tips allowed for fast and convenient sampling and ionization for mass spectrometry analysis by the BP-ESI-MS method. PMID:27111601

Evidence of the seismo-ionospheric precursor (SIP) is reported by statistically investigating the relationship between the total electron content (TEC) in global ionosphere map (GIM) and 56 M ⩾ 6.0 earthquakes during 1998-2013 in China. A median-based method together with the z test is employed to examine the TEC variations 30 days before and after the earthquake. It is found that the TEC significantly decreases 0600-1000 LT 1-6 days before the earthquake, and anomalously increases in 3 time periods of 1300-1700 LT 12-15 days; 0000-0500 LT 15-17 days; and 0500-0900 LT 22-28 days before the earthquake. The receiver operating characteristic (ROC) curve is then used to evaluate the efficiency of TEC for predicting M ⩾ 6.0 earthquakes in China during a specified time period. Statistical results suggest that the SIP is the significant TEC reduction in the morning period of 0600-1000 LT. The SIP is further confirmed since the area under the ROC curve is positively associated with the earthquake magnitude.

The flow-duration curve is a cumulative frequency curve that shows the percent of time specified discharges were equaled or exceeded during a given period. It combines in one curve the flow characteristics of a stream throughout the range of discharge, without regard to the sequence of occurrence. If the period upon which the curve is based represents the long-term flow of a stream, the curve may be used to predict the distribution of future flows for water- power, water-supply, and pollution studies. This report shows that differences in geology affect the low-flow ends of flow-duration curves of streams in adjacent basins. Thus, duration curves are useful in appraising the geologic characteristics of drainage basins. A method for adjusting flow-duration curves of short periods to represent long-term conditions is presented. The adjustment is made by correlating the records of a short-term station with those of a long-term station.

Variable responses are fundamental for all experiments, and they can consist of information-rich, redundant, and low signal intensities. A dataset can consist of a collection of variable responses over multiple classes or groups. Usually some of the variables are removed in a dataset that contain very little information. Sometimes all the variables are used in the data analysis phase. It is common practice to discriminate between two distributions of data; however, there is no formal algorithm to arrive at a degree of separation (DS) between two distributions of data. The DS is defined herein as the average of the sum of the areas from the probability density functions (PDFs) of A and B that contain a≥percentage of A and/or B. Thus, DS90 is the average of the sum of the PDF areas of A and B that contain ≥90% of A and/or B. To arrive at a DS value, two synthesized PDFs or very large experimental datasets are required. Experimentally it is common practice to generate relatively small datasets. Therefore, the challenge was to find a statistical parameter that can be used on small datasets to estimate and highly correlate with the DS90 parameter. Established statistical methods include the overlap area of the two data distribution profiles, Welch's t-test, Kolmogorov-Smirnov (K-S) test, Mann-Whitney-Wilcoxon test, and the area under the receiver operating characteristics (ROC) curve (AUC). The area between the ROC curve and diagonal (ACD) and the length of the ROC curve (LROC) are introduced. The established, ACD, and LROC methods were correlated to the DS90 when applied on many pairs of synthesized PDFs. The LROC method provided the best linear correlation with, and estimation of, the DS90. The estimated DS90 from the LROC (DS90-LROC) is applied to a database, as an example, of three Italian wines consisting of thirteen variable responses for variable ranking consideration. An important highlight of the DS90-LROC method is utilizing the LROC curve methodology to

The rocking curves (RCs) for MoK{sub α1} and MoK{sub α2} characteristic X-ray lines have been experimentally and theoretically studied in the nondispersive scheme of an X-ray double-crystal TPC-K diffractometer. The results of measurements and theoretical calculations of double-crystal RCs for characteristic X-rays from tubes with a molybdenum anode and different widths of slits show that a decrease in the slit width leads to an increase in the relative contribution of the MoK{sub α2}-line RC in comparison with the intensity of the tails of the MoK{sub α1}-line RC. It is shown that the second peak of the MoK{sub α2} line becomes increasingly pronounced in the tail of the MoK{sub α1}-line RC with a decrease in the slit width. Two plane-parallel Si plates (input faces (110), diffraction vector h 〈220〉) were used as a monochromator crystal and a sample. The results of measuring double-crystal RCs are in good agreement with theoretical calculations.

Sericin is a proteinous substrate that envelops fibroin (silk) fiber, and its recovery provides significant economical and social benefits. Sericin is an antibacterial agent that resists oxidation and absorbs moisture and UV light. In powder form, sericin has a wide range of applications in food, cosmetics and drug delivery. Asides from other techniques of producing powder, such as precipitation and spray drying, electrospraying can yield solid nanoparticles, particularly in the submicron range. Here, we report the production of sericin nanopowder by electrospraying. Sericin sponge was recovered from Bombyx mori cocoons through a high-temperature, high-pressure process, followed by centrifugation and freeze drying of the sericin solution. The electrospraying solution was prepared by dissolving the sericin sponge in dimethyl sulfoxide. We demonstrate that electrospraying is capable of producing sericin nanopowder with an average particle size of 25 nm, which is by far smaller than the particles produced by other techniques. The electrosprayed sericin nanopowder consists of small crystallites and exhibits a high moisture absorbance.

This study quantitatively evaluated the performance of the exponential transformation of the free-response operating characteristiccurve (EFROC) metric, with the Channelized Hotelling Observer (CHO) as a reference. The CHO has been used for image quality assessment of reconstruction algorithms and imaging systems and often it is applied to study the signal-location-known cases. The CHO also requires a large set of images to estimate the covariance matrix. In terms of clinical applications, this assumption and requirement may be unrealistic. The newly developed location-unknown EFROC detectability metric is estimated from the confidence scores reported by a model observer. Unlike the CHO, EFROC does not require a channelization step and is a non-parametric detectability metric. There are few quantitative studies available on application of the EFROC metric, most of which are based on simulation data. This study investigated the EFROC metric using experimental CT data. A phantom with four low contrast objects: 3mm (14 HU), 5mm (7HU), 7mm (5 HU) and 10 mm (3 HU) was scanned at dose levels ranging from 25 mAs to 270 mAs and reconstructed using filtered backprojection. The area under the curve values for CHO (AUC) and EFROC (AFE) were plotted with respect to different dose levels. The number of images required to estimate the non-parametric AFE metric was calculated for varying tasks and found to be less than the number of images required for parametric CHO estimation. The AFE metric was found to be more sensitive to changes in dose than the CHO metric. This increased sensitivity and the assumption of unknown signal location may be useful for investigating and optimizing CT imaging methods. Future work is required to validate the AFE metric against human observers.

A new method of electrospray-assisted laser desorption/ionization (ELDI) mass spectrometry, which combines laser desorption with post-ionization by electrospray, was applied to rapid analysis of solid materials under ambient conditions. Analytes were desorbed from solid metallic and insulating substrata using a pulsed nitrogen laser. Post-ionization produced high-quality mass spectra characteristic of electrospray, including protein multiple charging. For the first time, mass spectra of intact proteins were obtained using laser desorption without adding a matrix. Bovine cytochrome c and an illicit drug containing methaqualone were chosen in this study to demonstrate the applicability of ELDI to the analysis of proteins and synthetic organic compounds. PMID:16299699

Two experiments were conducted to fit growth curves, and determine age-related changes in carcass characteristics, organs, serum biochemical parameters, and gene expression of intestinal nutrient transporters in domestic pigeon (Columba livia). In experiment 1, body weight (BW) of 30 pigeons was respectively determined at 1, 3, 7, 14, 21, 28, and 35 days old to fit growth curves and to describe the growth of pigeons. In experiment 2, eighty-four 1-day-old squabs were grouped by weight into 7 groups. On d 1, 3, 7, 14, 21, 28, and 35, twelve birds from each group were randomly selected for slaughter and post-slaughter analysis. The results showed that BW of pigeons increased rapidly from d 1 to d 28 (a 25.7-fold increase), and then had little change until d 35. The Logistic, Gompertz, and Von Bertalanffy functions can all be well fitted with the growth curve of domestic pigeons (R2>0.90) and the Gompertz model showed the highest R2value among the models (R2=0.9997). The equation of Gompertz model was Y=507.72×e-(3.76exp(-0.17t))(Y=BW of pigeon (g); t=time (day)). In addition, breast meat yield (%) increased with age throughout the experiment, whereas the leg meat yield (%) reached to the peak on d 14. Serum total protein, albumin, globulin, and glucose concentration were increased with age, whereas serum uric acid concentration was decreased (P<0.05). Furthermore, the gene expressions of nutrient transporters (y+LAT2, LAT1, B0AT1, PepT1, and NHE2) in jejunum of pigeon were increased with age. The results of correlation analysis showed the gene expressions of B0AT1, PepT1, and NHE2 had positive correlations with BW (0.73

The present invention is an interface between a capillary electrophoresis separation capillary end and an electrospray ionization mass spectrometry emitter capillary end, for transporting an analyte sample from a capillary electrophoresis separation capillary to a electrospray ionization mass spectrometry emitter capillary. The interface of the present invention has: (a) a charge transfer fitting enclosing both of the capillary electrophoresis capillary end and the electrospray ionization mass spectrometry emitter capillary end; (b) a reservoir containing an electrolyte surrounding the charge transfer fitting; and (c) an electrode immersed into the electrolyte, the electrode closing a capillary electrophoresis circuit and providing charge transfer across the charge transfer fitting while avoiding substantial bulk fluid transfer across the charge transfer fitting. Advantages of the present invention have been demonstrated as effective in providing high sensitivity and efficient analyses.

The present invention is an interface between a capillary electrophoresis separation capillary end and an electrospray ionization mass spectrometry emitter capillary end, for transporting an anolyte sample from a capillary electrophoresis separation capillary to a electrospray ionization mass spectrometry emitter capillary. The interface of the present invention has: (a) a charge transfer fitting enclosing both of the capillary electrophoresis capillary end and the electrospray ionization mass spectrometry emitter capillary end; (b) a reservoir containing an electrolyte surrounding the charge transfer fitting; and (c) an electrode immersed into the electrolyte, the electrode closing a capillary electrophoresis circuit and providing charge transfer across the charge transfer fitting while avoiding substantial bulk fluid transfer across the charge transfer fitting. Advantages of the present invention have been demonstrated as effective in providing high sensitivity and efficient analyses.

Electrosprays are a powerful technique to generate charged micro/nanodroplets. In the last century, the technique has been extensively studied, developed, and recognized with a shared Nobel price in Chemistry in 2002 for its wide spread application in mass spectrometry. However, nowadays techniques based on microfluidic devices are competing to be the next generation in atomization techniques. Therefore, an interesting development would be to integrate the electrospray technique into a microfluidic liquid-liquid device. Several works in the literature have attempted to build a microfluidic electrospray with disputable results. The main problem for its integration is the lack of knowledge of the working parameters of the liquid-liquid electrospray. The “submerged electrosprays” share similar properties as their counterparts in air. However, in the microfluidic generation of micro/nanodroplets, the liquid-liquid interfaces are normally stabilized with surface active agents, which might have critical effects on the electrospray behavior. In this work, we review the main properties of the submerged electrosprays in liquid baths with no surfactant, and we methodically study the behavior of the system for increasing surfactant concentrations. The different regimes found are then analyzed and compared with both classical and more recent experimental, theoretical and numerical studies. A very rich phenomenology is found when the surface tension is allowed to vary in the system. More concretely, the lower states of electrification achieved with the reduced surface tension regimes might be of interest in biological or biomedical applications in which excessive electrification can be hazardous for the encapsulated entities. PMID:24155865

Two-phase sampling design, where biomarkers are subsampled from a phase-one cohort sample representative of the target population, has become the gold standard in biomarker evaluation. Many two-phase case-control studies involve biased sampling of cases and/or controls in the second phase. For example, controls are often frequency-matched to cases with respect to other covariates. Ignoring biased sampling of cases and/or controls can lead to biased inference regarding biomarkers' classification accuracy. Considering the problems of estimating and comparing the area under the receiver operating characteristicscurve (AUC) for a binary disease outcome, the impact of biased sampling of cases and/or controls on inference and the strategy to efficiently account for the sampling scheme have not been well studied. In this project, we investigate the inverse-probability-weighted method to adjust for biased sampling in estimating and comparing AUC. Asymptotic properties of the estimator and its inference procedure are developed for both Bernoulli sampling and finite-population stratified sampling. In simulation studies, the weighted estimators provide valid inference for estimation and hypothesis testing, while the standard empirical estimators can generate invalid inference. We demonstrate the use of the analytical variance formula for optimizing sampling schemes in biomarker study design and the application of the proposed AUC estimators to examples in HIV vaccine research and prostate cancer research. PMID:26883772

Two-phase sampling design, where biomarkers are subsampled from a phase-one cohort sample representative of the target population, has become the gold standard in biomarker evaluation. Many two-phase case–control studies involve biased sampling of cases and/or controls in the second phase. For example, controls are often frequency-matched to cases with respect to other covariates. Ignoring biased sampling of cases and/or controls can lead to biased inference regarding biomarkers' classification accuracy. Considering the problems of estimating and comparing the area under the receiver operating characteristicscurve (AUC) for a binary disease outcome, the impact of biased sampling of cases and/or controls on inference and the strategy to efficiently account for the sampling scheme have not been well studied. In this project, we investigate the inverse-probability-weighted method to adjust for biased sampling in estimating and comparing AUC. Asymptotic properties of the estimator and its inference procedure are developed for both Bernoulli sampling and finite-population stratified sampling. In simulation studies, the weighted estimators provide valid inference for estimation and hypothesis testing, while the standard empirical estimators can generate invalid inference. We demonstrate the use of the analytical variance formula for optimizing sampling schemes in biomarker study design and the application of the proposed AUC estimators to examples in HIV vaccine research and prostate cancer research. PMID:26883772

Autism Spectrum Disorders (ASD) are a heterogeneous group of neurodevelopmental disorders. Recognized causes of ASD include genetic factors, metabolic diseases, toxic and environmental factors, and a combination of these. Available tests fail to recognize genetic abnormalities in about 70% of ASD children, where diagnosis is solely based on behavioral signs and symptoms, which are difficult to evaluate in very young children. Although it is advisable that specific psychotherapeutic and pedagogic interventions are initiated as early as possible, early diagnosis is hampered by the lack of nongenetic specific biological markers. In the past ten years, the scientific literature has reported dozens of neurophysiological and biochemical alterations in ASD children; however no real biomarker has emerged. Such literature is here reviewed in the light of Receiver Operating Characteristic (ROC) analysis, a very valuable statistical tool, which evaluates the sensitivity and the specificity of biomarkers to be used in diagnostic decision making. We also apply ROC analysis to some of our previously published data and discuss the increased diagnostic value of combining more variables in one ROC curve analysis. We also discuss the use of biomarkers as a tool for advancing our understanding of nonsyndromic ASD. PMID:26648598

Several spherically curved microchannel plate (MCP) stack configurations were studied as part of an ongoing astrophysical detector development program, and as part of the development of the ALEXIS satellite payload. MCP pairs with surface radii of curvature as small as 7 cm, and diameters up to 46 mm have been evaluated. The experiments show that the gain (greater than 1.5 x 10 exp 7) and background characteristics (about 0.5 events/sq cm per sec) of highly curved MCP stacks are in general equivalent to the performance achieved with flat MCP stacks of similar configuration. However, gain variations across the curved MCP's due to variations in the channel length to diameter ratio are observed. The overall pulse height distribution of a highly curved surface MCP stack (greater than 50 percent FWHM) is thus broader than its flat counterpart (less than 30 percent). Preconditioning of curved MCP stacks gives comparable results to flat MCP stacks, but it also decreases the overall gain variations. Flat fields of curved MCP stacks have the same general characteristics as flat MCP stacks.

Discussion of informetric distributions shows that generalized Leimkuhler functions give proper fits to a large variety of Bradford curves, including those exhibiting a Groos droop or a rising tail. The Kolmogorov-Smirnov test is used to test goodness of fit, and least-square fits are compared with Egghe's method. (Contains 53 references.) (LRW)

Experiments were conducted in order to study and characterize electrohydrodynamic atomization in the simple-jet mode for inviscid liquids. The operational window of this mode regarding the electric potential and liquid flow rate is presented. From the data it could be concluded that this mode can be divided by the characteristics of its breakup mechanism and that these characteristics are a function of the liquid Weber number and the electric Bond number for a given setup. Additionally we were also able to calculate the average charge per droplet and define the average size of primary and satellite droplets. The dispersion of the spray was also studied regarding its relation to the liquid Weber number and to the electric Bond number. We conclude that simple-jet mode electrosprays are a good option for applications which require monodisperse micrometer droplets with high throughput. PMID:23368048

An improvement to the system and method for analyzing molecular constituents of a composition sample that comprises improvements to an electrospray ionization source for interfacing to mass spectrometers and other detection devices. The improvement consists of establishing a unique electrical circuit pattern and nozzle configuration, a metallic coated and conical shaped capillary outlet, coupled with sizing of the capillary to obtain maximum sensitivity.

This paper aims to assess the functional and spatial variability in the response of CO2 exchange to irradiance across the Arctic tundra during peak season using light response curve (LRC) parameters. This investigation allows us to better understand the future response of Arctic tundra under climatic change. Data was collected using the micrometeorological eddy covariance technique from 12 circumpolar Arctic tundra sites, in the range of 64-74° N. The LRCs were generated for 14 days with peak net ecosystem exchange (NEE) using an NEE -irradiance model. Parameters from LRCs represent site specific traits and characteristics describing: (a) NEE at light saturation (Fcsat), (b) dark respiration (Rd), (c) light use efficiency (α), (d) NEE when light is at 1000 μmol m-2 s-1 (Fc1000), (e) potential photosynthesis at light saturation (Psat) and (f) the light compensation point (LCP). Parameterization of LRCs was successful in predicting CO2 flux dynamics across the Arctic tundra. Yet we did not find any trends in LRC parameters across the whole Arctic tundra but there were indications for temperature and latitudinal differences within sub-regions like Russia and Greenland. Together, LAI and July temperature had a high explanatory power of the variance in assimilation parameters (Fcsat, Fc1000 and Psat), thus illustrating the potential for upscaling CO2 exchange for the whole Arctic tundra. Dark respiration was more variable and less correlated to environmental drivers than was assimilation parameters. Thus, indicating the inherent need to include other parameters such as nutrient availability, substrate quantity and quality in flux monitoring activities.

This paper aims to assess the spatial variability in the response of CO2 exchange to irradiance across the Arctic tundra during peak season using light response curve (LRC) parameters. This investigation allows us to better understand the future response of Arctic tundra under climatic change. Peak season data were collected during different years (between 1998 and 2010) using the micrometeorological eddy covariance technique from 12 circumpolar Arctic tundra sites, in the range of 64-74° N. The LRCs were generated for 14 days with peak net ecosystem exchange (NEE) using an NEE-irradiance model. Parameters from LRCs represent site-specific traits and characteristics describing the following: (a) NEE at light saturation (Fcsat), (b) dark respiration (Rd), (c) light use efficiency (α), (d) NEE when light is at 1000 μmol m-2 s-1 (Fc1000), (e) potential photosynthesis at light saturation (Psat) and (f) the light compensation point (LCP). Parameterization of LRCs was successful in predicting CO2 flux dynamics across the Arctic tundra. We did not find any trends in LRC parameters across the whole Arctic tundra but there were indications for temperature and latitudinal differences within sub-regions like Russia and Greenland. Together, leaf area index (LAI) and July temperature had a high explanatory power of the variance in assimilation parameters (Fcsat, Fc1000 and Psat, thus illustrating the potential for upscaling CO2 exchange for the whole Arctic tundra. Dark respiration was more variable and less correlated to environmental drivers than were assimilation parameters. This indicates the inherent need to include other parameters such as nutrient availability, substrate quantity and quality in flux monitoring activities.

Resiquimod is a Toll-like receptor (TLR) 7/8 agonist that has previously been used as a vaccine adjuvant, as a topical treatment of viral lesions and skin cancer, and as an antiviral treatment. We report on the combined application of remote loading and electrospray to produce liposomal resiquimod, with the broader goals of improving drug encapsulation efficiency and scalability of liposome production methods. Drug loading in liposomes increased from less than 1% to greater that 3% by mass when remote loading was used, whether the liposomes were generated by thin-film hydration or electrospray methods. Dynamic light scattering (DLS) determined mean vesicle diameters of 137 ± 11 nm and 103 ± 4 for the thin-film and electrospray methods, respectively. Transmission electron microscopy (TEM) images showed spherical vesicles with sizes consistent with the DLS measurements. In vitro drug release profiles found that most of the drug remained within the liposomes at both pH 5.5 and 7.4. The in vitro bioactivity of the liposomal drug was also demonstrated by the increase in nitrite production when RAW macrophages were exposed to the drug. Our findings indicate that the remotely loaded liposomes formed via the scalable electrospray method have characteristics comparable to those produced via conventional batch methods. The methods discussed here are not limited to the enhanced delivery of resiquimod. Rather, they should be readily adaptable to other compounds compatible with remote loading. PMID:26568143

An improvement to the system and method is disclosed for analyzing molecular constituents of a composition sample that comprises improvements to an electrospray ionization source for interfacing to mass spectrometers and other detection devices. The improvement consists of establishing a unique electrical circuit pattern and nozzle configuration, a metallic coated and conical shaped capillary outlet, coupled with sizing of the capillary to obtain maximum sensitivity. 10 figs.

Recent work by Zenobi and colleagues [H. Chen, A. Wortmann, W. Zhang, R. Zenobi, Angew. Chem. Int. Ed. 46 (2007) 580] reports that human breath charged by contact with an electrospray (ES) cloud yields many mass peaks of species such as urea, glucose, and other ions, some with molecular weights above 1000 Da. All these species are presumed to be involatile, and to originate from breath aerosols by so-called extractive electrospray ionization EESI [H. Chen, A. Venter, R.G. Cooks, Chem. Commun. (2006) 2042]. However, prior work by Fenn and colleagues [C.M. Whitehouse, F. Levin, C.K. Meng, J.B. Fenn, Proceedings of the 34th ASMS Conference on Mass Spectrometry and Allied Topics, Denver, 1986 p. 507; S. Fuerstenau, P. Kiselev, J.B. Fenn, Proceedings of the 47th ASMS Conference on Mass Spectrometry, 1999, Dallas, TX, 1999] and by Hill and colleagues [C. Wu, W.F. Siems, H.H. Hill Jr., Anal. Chem. 72 (2000) 396] have reported the ability of electrospray drops to ionize a variety of low vapor pressure substances directly from the gas phase, without an apparent need for the vapor to be brought into the charging ES in aerosol form. The Ph.D. Thesis of Martínez-Lozano [P. Martínez-Lozano Sinués, Ph.D. Thesis, Department of Thermal and Fluid Engineering, University Carlos III of Madrid; April 5, 2006 (in Spanish); http://hdl.handle.net/10016/655] had also previously argued that the numerous human breath species observed via a similar ES ionization approach were in fact ionized directly from the vapor. Here, we observe that passage of the breath stream through a submicron filter does not eliminate the majority of the breath vapors seen in the absence of the filter. We conclude that direct vapor charging is the leading mechanism in breath ionization by electrospray drops, though aerosol ionization may also play a role.

Electrospray of nanoparticle inks is of great importance to the manufacturing of functional materials. In this study, we develop a new three-dimensional multiphysics method to model the electrospray of colloidal suspension to a flat substrate. The Lagrangian Particle Tracking (LPT) transport equation is coupled to mass and heat transfer using convective droplet vaporization model, which allow us to track each particle-laden ink droplets and dry nanoparticles in the electrospray plume and probe the deposit structures. Herein, we consider dilute inks that are experimentally relevant, assuming monodisperse nanoparticles. We characterize the overall statistics of the plume and the dynamics of individual ink droplet or dry nanoparticle. It is shown that the segregation effect affects not only primary and satellite droplets but also dry nanoparticles. We observe nanoparticles deposit structure changing process, in particular time evolution of the density profile along radial direction. Our results show that the region of high nanoparticle density transitioning from only the edge to both the edge and center, which agrees with previous experimental studies.

The phenomenon of electrospraying of liquids is presented from the perspective of the electrochemistry involved. Basics of current and liquid flow in the capillary and spray tip are discussed, followed by specifics of charging and discharging of the sprayed liquid surface. Fundamental theories and numerical modeling relating electrospray current to solution and spray parameters are described and then compared with our own experimentally obtained data. The method of mapping potentials and currents inside the electrospray capillary by using an inserted electrically-isolated small wire probe electrode is discussed in detail with illustrations from new and published data. Based on these experimentally obtained results, a new mathematical model is derived. The introduced "nonlinear resistor electrospray capillary model" divides the electrospray capillary into small sections, adds their contributions, and then, by transition to infinitely small section thickness, produces analytical formulas that relate current and potential maps to other properties of the electrospraying liquid: primarily conductivity and current density. The presentation of the model is undertaken from an elementary standpoint, and it offers the possibility to obtain quantitative information regarding operating parameters from typical analytical systems subjected to electrospray. The model stresses simplicity and ease of use; examples applying experimental data are shown and some predictions of the model are also presented. The developed nonlinear resistor electrospray capillary model is intended to provide a new quantitative basis for improving the understanding of electrochemical transformations occurring in the electrospray emitter. A supplemental material section gives full derivation of the model and discusses other consequences.

This study purports that parental rejection and warmth are critical to the development of adolescent drug use, and investigates a model that also considers children's vulnerability and deviant peer affiliations. It tests mediation through the proximal risk factor of deviant peers. Poisson growth curve modeling was used to examine participants from…

In an electrospray, high electric potentials are utilized to generate a fine aerosol of a conductive solvent. For this study, the solvent consisted of nanoparticles dispersed in alcohol. The nanoparticle suspensions act as printable nanoparticle inks. In this process, a glass capillary tube is held as a high electric potential relative to a grounded reference plate located below the tip. Droplets are ejected from the tube and are directed towards the ground plate. If the solvent is sufficiently volatile, it will rapidly evaporate while the droplets are in flight (due to the high surface area to volume ratio) leaving behind dry, highly charged nanoparticles. The droplets/nanoparticles are deposited onto a target substrate that is place onto the grounded plate. The transport of any individual droplet/nanoparticle from the emitter tip to the target substrate is a stochastic process. This transport can be modeled using a Monte Carlo simulation. The probability of an individual particle being deposited at a given location on the target substrate is directly related to the electric potential at that location. In other words, the probability function that determines the deposition is directly related to the electric potential at the substrate. The total potential is comprised of the applied electric potential required to generate the electrospray, the induced charge on the surface of the target dielectric, and the charge on the individual particles themselves. We report on the structure of droplet/nanoparticle deposits printed using electrospray. The evolution of the deposit is investigated over time using experimental studies and Monte Carlo simulations. The deposit structure passes through four distinct regimes that are characterized by repeatable bulk features.

Liquid fuel dispersion in practical systems is typically achieved by spraying the fuel into a polydisperse distribution of droplets evaporating and burning in a turbulent gaseous environment. In view of the nearly unsurmountable difficulties of this two-phase flow, it would be useful to use an experimental arrangement that allow a systematic study of spray evolution and burning in configurations of gradually increasing levels of complexity, starting from laminar sprays to fully turbulent ones. An Electrostatic Spray (ES) of charged droplets lends itself to this type of combustion experiments under well-defined conditions and can be used to synthesize gradually more complex spray environments. In its simplest configuration, a liquid is fed into a small metal tube maintained at several kilovolts relative to a ground electrode few centimeters away. Under the action of the electric field, the liquid meniscus at the outlet of the capillary takes a conical shape, with a thin jet emerging from the cone tip. This jet breaks up farther downstream into a fine spray of charged droplets. Several advantages distinguish the electrospray from alternative atomization techniques: the self-dispersion property of the spray due to coulombic repulsion; the absence of droplet coalescence; the potential control of the trajectories of charged droplets by suitable disposition of electrostatic fields; and the decoupling of atomization, which is strictly electrostatic, from gas flow processes. Furthermore, as recently shown in our laboratory, the electrospray can produce quasi-monodisperse droplets over a very broad size range (1-100 microns). The ultimate objective of this research project is to study the formation and burning of electrosprays of liquid fuels first in laminar regimes and then in turbulent ones. Combustion will eventually be investigated in conditions of three-dimensional droplet-droplet interaction, for which experimental studies have been limited to either qualitative

Coaxial electrospray is an electrohydrodynamic process that produces multilayer microparticles and nanoparticles by introducing coaxial electrified jets. In comparison with other microencapsulation/nanoencapsulation processes, coaxial electrospray has several potential advantages such as high encapsulation efficiency, effective protection of bioactivity and uniform size distribution. However, process control in coaxial electrospray is challenged by the multiphysical nature of the process and the complex interplay of multiple design, process and material parameters. This paper reviews the previous works and the recent advances in design, modeling and control of a coaxial electrospray process. The review intends to provide general guidance for coaxial electrospray and stimulate further research and development interests in this promising microencapsulation/nanoencapsulation process. PMID:23249155

Generation of nanoemulsions is of great interest in medical and pharmaceutical applications; drug delivery or antiviral emulsions are typical examples. The use of electrosprays for dispersing liquids inside liquid insulator baths have been recently reported, (Barrero et al. J. Colloid Interf. Sci. 272, 104, 2004). Capsules, nanotubes and coaxial nanofibers have been obtained from electrified coaxial jets (Loscertales et al. Science 295, n. 5560, 1695, 2002; J. American Chem. Soc. 126, 5376, 2004). Here we present a method for making double emulsions (both water-oil-water and o/w/o) based on the generation of compound electrosprays inside insulator liquid baths. Basically, a conducting liquid injected throughout a capillary needle is electroatomized in cone-jet mode inside a dielectric liquid bath. A third insulating liquid is injected inside the Taylor cone to form a second meniscus. Then, a steady coaxial jet, in which the insulating liquid is coated by the conducting one, develops. A double emulsion forms as a result of the jet breaking up into compound droplets electrically charged. Experimental results carried out with glycerine and different oils in a bath of heptane are reported.

In coaxial jet electrosprays inside liquid baths, a conductive liquid forms a cone-jet electrospray in a bath containing a dielectric liquid. An additional dielectric liquid is injected inside the Taylor cone forming a liquid meniscus. In certain circumstances, however, we have observed that the dielectric menisci present extremely sharp tips, without mass emission, that can be stabilized and made completely steady. In this presentation we will first explore the parametrical range of liquid properties, mainly viscosities and surface tensions, under which these sharp tips take place. Secondly, we have developed a simple analytical model for the very complex electro-hydrodynamical flow, which predicts the angle of the tip as a function of the liquid properties. Therefore, we are able to compare it with the results of the experiments. When the liquid meniscus is slowly fed, the cusped interface turns into a spout which flows coated by the conducting liquid forming the electrified coaxial jet which has been successfully employed for the production of double emulsions (Marin et al., Phys. Rev. Lett. 98, 014502, 2007).

The thermoluminescence (TL) glow curves and kinetics parameters of Thulium (Tm) doped silica cylindrical fibers (CF) are presented. A linear accelerator (LINAC) was used to deliver high-energy radiation of 21MeV electrons and 10MV photons. The CFs were irradiated in the dose range of 0.2-10Gy. The experimental glow curve data was reconstructed by using WinREMS. The WinGCF software was used for the kinetic parameters evaluation. The TL sensitivity of Tm-doped silica CF is about 2 times higher as compared to pure silica CF. Tm-doped silica CF seems to be more sensitive to 21MeV electrons than to 10MV photons. Surprisingly, no supralinearity was displayed and a sub-linear response of Tm-doped silica CF was observed within the analyzed dose range for both 21MeV electrons and 10MV photons. The Tm-doped silica CF glow curve consists of 5 individual glow peaks. The Ea of peak 4 and peak 5 was highly dependent on dose when irradiated with photons. We also noticed that the electron radiation (21MeV) caused a shift of glow peak by 7-13°C to the higher temperature region compared with photons radiation (10MV). Our Tm-doped fibers seem to give high TL response after 21MeV electrons, which gives around 2 times higher peak integral as compared with 10MV photon radiation. We concluded that peak 4 is the first-order kinetic peak and can be used as the main dosimetric peak of Tm-doped silica CF. PMID:25644081

This volume, a reprinting of a classic first published in 1952, presents detailed discussions of 26 curves or families of curves, and 17 analytic systems of curves. For each curve the author provides a historical note, a sketch or sketches, a description of the curve, a discussion of pertinent facts, and a bibliography. Depending upon the curve,…

1. The onset of lay, quality of eggs during early lay and gonadal development of both sexes were analysed in meat-type lines of Japanese quail, HG and LG divergently selected for high and low relative weight gain between 11 and 28 d of age, respectively, and constant body weight (BW) at 49 d of age. 2. The LG line was sexually mature at an earlier age and lower BW than the HG line. This corresponded with the trend during embryonic and early postnatal development. 3. Analysis of gonads also confirmed earlier sexual development in the LG than in the HG line. In both lines, the growth of testes was detected about one week earlier than the growth of ovary. 4. Despite the different age and BW at onset of lay, HG and LG quail commenced lay at the same degree of maturity (about 90% of adult BW). This implied that the onset of sexual maturity could be identified as a point on the growth curve which terminates the linear phase. 5. When compared with the LG line, the HG line was characterised by a longer acceleration and shorter retardation phase of the growth curve. This difference is seen as an important determinant of line differences in growth and reproductive performance. PMID:17952726

The diagnostic accuracy of RN, CT, and MR imaging for AVN was determined retrospectively using ROC curves. The abnormal images were drawn from 35 patients who had proven AVN. The MR images were made using an experimental GE resistive magnet operating at 0.12 Tesla corresponding to a proton resonant of 5.1 MHz. Most of the CT images were made using a GE 9800 CT Scanner. RN images were obtained using 99m-Tc MDP. Planar as well as pinhole images of both hips were acquired on each case. Three test sets, one for each modality was assembled. Each of the imaging modalities had a sensitivity of 85%, and a specificity of 85% at the optimal point on the ROC curve. These data demonstrates that MR imaging is not significantly different from other modalities for discrimination between AVN and normal hips. The test set did not include patients with disease other than AVN. The authors are planning to perform a blinded prospective study for more definitive results.

The ultraviolet aerodynamic particle sizer (UVAPS) is a novel commercially available aerosol spectrometer for real-time continuous monitoring of viable bioaerosols, based on fluorescence from living microorganisms. In a previous study, we developed an electrospray-assisted UVAPS using biological electrospray techniques, which have the advantage of generating non-agglomerated single particles by the repulsive electrical forces. With this electrospraying of suspensions containing microorganisms, the analytical system can supply more accurate and quantitative information about living microorganisms than with conventional aerosolization. Using electrospray-assisted UVAPS, we investigated the characteristics of bacterial particles with various viabilities in real-time. Escherichia coli was used as the test microorganism, and its initial viability was controlled by the degree of exposure to UV irradiation. In the stable cone-jet domain, the particle size distributions of test bacterial particles remained almost uniform regardless of the degree of UV inactivation. However, the fluorescence spectra of the bacterial particles changed with the degree of UV inactivation. The fluorescence characteristics of UV-inactivated bacterial particles tended to show a similar decline with viability, determined by the sampling and culture method, although the percentage showing fluorescence was higher than that showing viability. PMID:21621246

Nanoparticles preparation of Mefenamic acid (MA) by using an electrospray drying method was conducted in this study. Electrospray drying is a process that uses electrostatic force to disperse a conductive liquid stream into fine charged droplets through the coulomb fission of charges in the liquid and finally dry into fine particles. Electrospray drying modes operation usually in Taylor cone jet, and it was formed by controlling applied voltage and liquid flow rate. A conductive liquid (2.77–8.55μScm{sup −1}) which is MA solution was prepared by using acetone with concentration 0.041 and 0.055 M before pumping at a flow rate of 3–6ml/h. By applying the applied voltage at 1.3–1.5 kV, Taylor cone jet mode was formed prior to the electrospray. During electrospray drying process, solvent evaporation from the droplet was occurring that leads to coulomb disruption and may generate to nanoparticles. The dried nanoparticles were collected on a grounded substrate that was placed at varying distance from the electrospray. MA particle with size range of 100–400 nm were produced by electrospray drying process. Characterization of particles by using X-ray diffractometry (XRD) and differential scanning calorimetry (DSC) show that particles formed into polymorph I.

In desorption electrospray ionisation (DESI) the interaction between the electrospray and the surface is key to two important analytical parameters, the spatial resolution and the sensitivity. We evaluate the effect of the electrospray solvent type, organic solvent fraction with water, analyte solubility and substrate wettability on DESI erosion diameter and material transferral into useful ion signal. To do this five amino acids, glycine, alanine, valine, leucine and phenylalanine are prepared as thin films on three substrates, UV/ozone treated glass, glass and polytetrafluoroethylene (PTFE). Four different solvents, acetonitrile (ACN), methanol (MeOH), ethanol (EtOH) and propan-2-ol (IPA), are used with organic solvent fractions with water varying from 0.1 to 1. These model systems allow the solubility or wettability to be kept constant as other parameters are varied. Additionally, comparison with electrospray ionisation (ESI) allows effects of ionisation efficiency to be determined. It is shown that the DESI efficiency is linearly dependent on the solubility (for these materials at least) and for analytes with solubilities below 1.5 g kg(-1), additional strategies may be required for DESI to be effective. We show that the DESI erosion diameter improves linearly with organic solvent fraction, with an organic solvent fraction of 0.9 instead of 0.5 leading to a 2 fold improvement. Furthermore, this leads to a 35 fold increase in DESI efficiency, defined as the molecular ion yield per unit area. It is shown that these improvements correlate with smaller droplet sizes rather than surface wetting or ionisation. PMID:20349538

A system and method for analyzing molecular constituents of a composition sample include: forming a solution of the sample, separating the solution by capillary electrophoresis into an eluent of constituents longitudinally separated according to their relative electrophoretic mobilities, electrospraying the eluent to form a charged spray in which the molecular constituents have a temporal distribution; and detecting or collecting the separated constituents in accordance with the temporal distribution in the spray. A first high-voltage (e.g., 5--100 kVDC) is applied to the solution. The spray is charged by applying a second high voltage (e.g.,{+-}2--8 kVDC) between the eluent at the capillary exit and a cathode spaced in front of the exit. A complete electrical circuit is formed by a conductor which directly contacts the eluent at the capillary exit, or by conduction through a sheath electrode discharged in an annular sheath flow about the capillary exit. 21 figs.

A system and method for analyzing molecular constituents of a composition sample includes: forming a solution of the sample, separating the solution by capillary electrophoresis into an eluent of constituents longitudinally separated according to their relative electrophoretic mobilities, electrospraying the eluent to form a charged spray in which the molecular constituents have a temporal distribution; and detecting or collecting the separated constituents in accordance with the temporal distribution in the spray. A first high-voltage (e.g., 5--100 kVDC) is applied to the solution. The spray is charged by applying a second high voltage (e.g., [+-]2--8 kVDC) between the eluent at the capillary exit and a cathode spaced in front of the exit. A complete electrical circuit is formed by a conductor which directly contacts the eluent at the capillary exit, or by conduction through a sheath electrode discharged in an annular sheath flow about the capillary exit. 21 figs.

A system and method for analyzing molecular constituents of a composition sample includes: forming a solution of the sample, separating the solution by capillary electrophoresis into an eluent of constituents longitudinally separated according to their relative electrophoretic mobilities, electrospraying the eluent to form a charged spray in which the molecular constituents have a temporal distribution; and detecting or collecting the separated constituents in accordance with the temporal distribution in the spray. A first high-voltage (e.g., 5-100 KVDC) is applied to the solution. The spray is charged by applying a second high voltage (e.g., .+-.2-8 KVDC) between the eluent at the capillary exit and a cathode spaced in front of the exit. A complete electrical circuit is formed by a conductor which directly contacts the eluent at the capillary exit, or by conduction through a sheath electrode discharged in an annular sheath flow about the capillary exit.

A system and method for analyzing molecular constituents of a composition sample includes: forming a solution of the sample, separating the solution by capillary electrophoresis into an eluent of constituents longitudinally separated according to their relative electrophoretic mobilities, electrospraying the eluent to form a charged spray in which the molecular constituents have a temporal distribution; and detecting or collecting the separated constituents in accordance with the temporal distribution in the spray. A first high-voltage (e.g., 5-100 KVDC) is applied to the solution. The spray is charged by applying a second high voltage (e.g., .+-.2-8 KVDC) between the eluent at the capillary exit and a cathode spaced in front of the exit. A complete electrical circuit is formed by a conductor which directly contacts the eluent at the capillary exit, or by conduction through a sheath electrode discharged in an annular sheath flow about the capillary exit.

Over the last 20 years, biological MS has changed out of all recognition. This is primarily due to the development in the 1980s of 'soft ionization' methods that permit the ionization and vaporization of large, polar, and thermally labile biomolecules. These developments in ionization mode have driven the design and manufacture of smaller and cheaper mass analysers, making the mass spectrometer a routine instrument in the biochemistry laboratory today. In the present review the revolutionary 'soft ionization' methods will be discussed with particular reference to electrospray. The mass analysis of ions will be described, and the concept of tandem MS introduced. Where appropriate, examples of the application of MS in biochemistry will be provided. Although the present review will concentrate on the MS of peptides/proteins and lipids, all classes of biomolecules can be analysed, and much excellent work has been done in the fields of carbohydrate and nucleic acid biochemistry. PMID:11311115

The objective of the study is to convince educational researchers of the necessity for "standard mastery curves" for the graphical representation of scores on summative tests for a group of students. Attention is drawn to the study of theoretical and empirical skew curves in education and biology. Use of standard mastery curves and study of skew…

Background Electrospray tandem mass spectrometry approach is widely used for the rapid characterization of natural products. This paper describes the gas-phased ESI-MS/MS fragmentation of abietane-type diterpenoids and their novel dimeric conjugate, salvialeriafone (1) using both positive and negative ion electrospray ionization quadropole time-of-flight mass spectrometry (ESI-QqTOF-MS/MS) hybrid instrument. Diterpenoids are widely distributed throughout the plant kingdom and posses interesting biological activities. Results ESI-QqTOF-MS (positive ion mode) of diterpenoids 1–6 under collision-induced dissociation tandem mass spectrometric analysis (CID-MS/MS) showed the characteristic losses of water, carbonmonoxide and propene molecules, while analysis in negative ion mode showed the characteristic losses of water, carbon monoxide, methane molecules and methyl radical. Results demonstrated the differences in the product ions and base peaks due to the differences in the skeleton. A novel dimeric conjugate, salvialeriafone (1) showed characteristic fragmentation pattern and was found to be more prone to form radical ions, as compared to monomeric diterpenoids. The fragmentation pathways of characteristic fragments were proposed with the aid of HRESIMS. Conclusions Extensive tandem mass spectrometric studies of salvialeriafone (1) and related diterpenoids 2–6 were conducted and their characteristic fragments were identified. The knowledge of the fragmentation pattern of these diterpenoids will be useful for the characterization of new dimers of this class of compounds. PMID:23079186

Some 20 x 20 aluminum panels were studied in a frequency range from 20 Hz to 5000 Hz. The noise sources used were a swept sine wave generator and a random noise generator. The effect of noise source was found to be negligible. Increasing the pressure differential across the panel gave better noise reduction below the fundamental resonance frequency due to an increase in stiffness. The largest increase occurred in the first 1 psi pressure differential. The curved, stiffened panel exhibited similar behavior, but with a lower increase of low frequency noise reduction. Depressurization on these panels resulted in decreased noise reduction at higher frequencies. The effect of damping tapes on the overall noise reduction values of the test specimens was small away from the resonance frequency. In the mass-law region, a slight and proportional improvement in noise reduction was observed by adding damping material. Adding sound absorbtion material to a panel with damping material beneficially increased noise reduction at high frequencies.

An investigation of thermocapillary effects on a heated, evaporating meniscus formed by a wetting liquid in a vertical capillary tube has been completed. Experiments were conducted to primarily observe how the wetting characteristics of the working fluid (pentane) are affected by the dynamics associated with the heating of and evaporation from a meniscus. The results have demonstrated that interfacial thermocapillary stresses arising from liquid-vapor interfacial temperature gradients can noticeably degrade the ability of the liquid to wet the pore.

We report low-cost conductometric gas sensors that use an ultrathin film made of graphene oxide (GO) nanoflakes as transducing element. The devices were fabricated by lift-off metallization and near-room temperature, atmospheric pressure electrospray printing using a shadow mask. The sensors are sensitive to reactive gases at room temperature without requiring any post heat treatment, harsh chemical reduction, or doping with metal nanoparticles. The sensors' response to humidity at atmospheric pressure tracks that of a commercial sensor, and is linear with changes in humidity in the 10%-60% relative humidity range while consuming <6 μW. Devices with GO layers printed by different deposition recipes yielded nearly identical response characteristics, suggesting that intrinsic properties of the film control the sensing mechanism. The gas sensors successfully detected ammonia at concentrations down to 500 ppm (absolute partial pressure of ∼5 × 10(-4) T) at ∼1 T pressure, room temperature conditions. The sensor technology can be used in a great variety of applications including air conditioning and sensing of reactive gas species in vacuum lines and abatement systems. PMID:26579701

We report low-cost conductometric gas sensors that use an ultrathin film made of graphene oxide (GO) nanoflakes as transducing element. The devices were fabricated by lift-off metallization and near-room temperature, atmospheric pressure electrospray printing using a shadow mask. The sensors are sensitive to reactive gases at room temperature without requiring any post heat treatment, harsh chemical reduction, or doping with metal nanoparticles. The sensors’ response to humidity at atmospheric pressure tracks that of a commercial sensor, and is linear with changes in humidity in the 10%-60% relative humidity range while consuming <6 μW. Devices with GO layers printed by different deposition recipes yielded nearly identical response characteristics, suggesting that intrinsic properties of the film control the sensing mechanism. The gas sensors successfully detected ammonia at concentrations down to 500 ppm (absolute partial pressure of ˜5 × 10-4 T) at ˜1 T pressure, room temperature conditions. The sensor technology can be used in a great variety of applications including air conditioning and sensing of reactive gas species in vacuum lines and abatement systems.

Low-voltage dielectric actuators (DEAs) can be fabricated using submicrometer-thin polydimethylsiloxane (PDMS) films. The two established techniques, namely spin coating and molecular beam deposition, however, are inappropriate to produce multistack DEAs in an efficient way. Therefore, we propose an alternative deposition technique, i.e., the alternating current electrospray deposition (ACESD) of 5 vol % PDMS in ethyl acetate solution and subsequent ultraviolet light curing. Atomic force microscopy makes possible the three-dimensional analysis of cured droplet-like islands. These circular islands, prepared on 2 in. Si(100) wafers from four polymers with molecular masses between 800 and 62 700 g/mol, reveal a characteristic morphology with an increasing height-to-diameter ratio. Using the 6000 g/mol polymer for ACESD, the film morphology evolution was tracked by applying conventional optical microscopy and spectroscopic ellipsometry. When the deposition was terminated after 13 s, circular islands with a mean height of 30 nm were found, while terminating the deposition after about 155 s led to a confluent layer with a mean height of 91 ± 10 nm. Potential electrostatic interactions between the droplets could not be identified through the analysis of spatial island distribution. Nevertheless, ACESD is a budget-priced and competitive deposition technique that can be employed to fabricate submicrometer-thin PDMS films with true nanometer roughness. PMID:26978236

In various embodiments, a method of laser ablation electrospray ionization mass spectrometry (LAESI-MS) may generally comprise micro-dissecting a cell comprising at least one of a cell wall and a cell membrane to expose at least one subcellular component therein, ablating the at least one subcellular component by an infrared laser pulse to form an ablation plume, intercepting the ablation plume by an electrospray plume to form ions, and detecting the ions by mass spectrometry.

Conics and Cartesian ovals are extremely important curves in various fields of science. In addition, aspheric curves based on conics are useful in optical design. Superconic curves, recently suggested by Greynolds, are extensions of both conics and Cartesian ovals and have been applied to optical design. However, they are not extensions of aspheric curves based on conics. In this work, we investigate another type of superconic curves. These superconic curves are extensions of not only conics and Cartesian ovals but also aspheric curves based on conics. Moreover, these are represented in explicit form, while Greynolds's superconic curves are in implicit form. PMID:27607506

The molecular weight of chitosan is one of its most determinant characteristics, which affects its processability and its performance as a biomaterial. However, information about the effect of this parameter on the formation of electrosprayed chitosan microcapsules is scarce. In this work, the impact of chitosan molecular weight on its electrosprayability was studied and correlated with its effect on the viscosity, surface tension and electrical conductivity of solutions. A Discriminant Function Analysis revealed that the morphology of the electrosprayed chitosan materials could be correctly predicted using these three parameters for almost 85% of the samples. The suitability of using electrosprayed chitosan capsules as carriers for bioactive agents was also assessed by loading them with a model active compound, (-)-epigallocatechin gallate (EGCG). This encapsulation, with an estimated efficiency of around 80% in terms of preserved antioxidant activity, showed the potential to prolong the antiviral activity of EGCG against murine norovirus via gradual bioactive release combined with its protection against degradation in simulated physiological conditions. PMID:27312621

A new concept for electrospray coupling of microfluidic devices with mass spectrometry was developed. The sampling orifice of the time-of-flight mass spectrometer was modified with an external adapter assisting in formation and transport of the electrosprayed plume from the multichannel polycarbonate microdevice. The compact disk sized microdevice was designed with radial channels extending to the circumference of the disk. The electrospray exit ports were formed by the channel openings on the surface of the disk rim. No additional tips at the channel exits were used. Electrospray was initiated directly from the channel openings by applying high voltage between sample wells and the entrance of the external adapter. The formation of the spatially unstable droplet at the electrospray openings was eliminated by air suction provided by a pump connected to the external adapter. Compared with the air intake through the original mass spectrometer sampling orifice, more than an order of magnitude higher flow rate was achieved for efficient transport of the electrospray plume into the mass spectrometer. Additional experiments with electric potentials applied between the entrance sections of the external adapter and the mass spectrometer indicated that the air flow was the dominant transport mechanism. Basic properties of the system were tested using mathematical modeling and characterized using ESI/TOF-MS measurements of peptide and protein samples. PMID:17102844

Quantitative determination of caffeine on reversed-phase C8 thin-layer chromatography plates using a surface sampling electrospray ionization system with tandem mass spectrometry detection is reported. The thin-layer chromatography/electrospray tandem mass spectrometry method employed a deuterium-labeled caffeine internal standard and selected reaction monitoring detection. Up to nine parallel caffeine bands on a single plate were sampled in a single surface scanning experiment requiring 35 min at a surface scan rate of 44 {mu}m/s. A reversed-phase HPLC/UV caffeine assay was developed in parallel to assess the mass spectrometry method performance. Limits of detection for the HPLC/UV and thin-layer chromatography/electrospray tandem mass spectrometry methods determined from the calibration curve statistics were 0.20 ng injected (0.50 {mu}L) and 1.0 ng spotted on the plate, respectively. Spike recoveries with standards and real samples ranged between 97 and 106% for both methods. The caffeine content of three diet soft drinks (Diet Coke, Diet Cherry Coke, Diet Pepsi) and three diet sport drinks (Diet Turbo Tea, Speed Stack Grape, Speed Stack Fruit Punch) was measured. The HPLC/UV and mass spectrometry determinations were in general agreement, and these values were consistent with the quoted values for two of the three diet colas. In the case of Diet Cherry Coke and the diet sports drinks, the determined caffeine amounts using both methods were consistently higher (by 8% or more) than the literature values.

We study the protein viability on Au nanoparticles during an electrospray and electrostatic-force-directed assembly process, through which Au nanoparticle-antibody conjugates are assembled onto the surface of carbon nanotubes (CNTs) to fabricate carbon nanotube field-effect transistor (CNTFET) biosensors. Enzyme-linked immunosorbent assay (ELISA) and field-effect transistor (FET) measurements have been used to investigate the antibody activity after the nanoparticle assembly. Upon the introduction of matching antigens, the colored reaction from the ELISA and the change in the electrical characteristic of the CNTFET device confirm that the antibody activity is preserved during the assembly process.

Extractive electrospray ionization (EESI) is a powerful ambient ionization technique that can provide comprehensive mass spectrometric (MS) information on aerosols, complex liquids, or suspensions without any sample pretreatment. An understanding of the EESI mechanism is critical for defining its range of application, the advantages, and limitations of EESI, and for improving its repeatability, sensitivity, and selectivity. However, no systematic study of EESI mechanisms has been conducted so far. In this work, fluorescence studies in the EESI plume using rhodamine 6G and H-acid sodium salt directly demonstrate that liquid-phase interactions occur between charged ESI droplets and neutral sample droplets. Moreover, the effect of the composition of the primary ESI spray and sample spray on signals of the analyte in EESI-MS was investigated systematically. The results show that the analyte signals strongly depend on its solubility in the solvents involved, indicating that selective extraction is the dominant mechanism involved in the EESI process. This mechanistic study provides valuable insights for optimizing the performance of EESI in future applications. PMID:20443546

Several distributions of small polynuclear ions of general form [nM + mA + pS]q+ (where M represents an alkaline earth cation (Mg, Ca, Sr or Ba), n = 2-10, A represents a halide, acetate or nitrate counterion originating in the divalent salt, and S represents an acetic acid or methanol adduct) are detected by FTICR when water/methanol solutions of alkaline earth salts are electrosprayed. For example, the largest cluster ion derived from 6.3 mM solutions of calcium acetate acidified with 2%x acetic acid have n= 10, m = 18, p = 5 and q = 2. Characteristics of these solutions suggest the presence of colloidal dispersions. These characteristics include stability upon aging, light scattering response and the requisite pre-etching of the glass containers. Aqueous mixtures of two group II salts produce mixed-salt cluster ions. For instance, from a mixture of calcium and magnesium acetate we trap mixed-cation clusters characterized by a complete set of binary partitions of n, for n = 2-6. Specifically, the manifold of clusters with four cations contains 4:0, 3:1, 2:2, 1:3 and 0:4 ratios of magnesium to calcium. Isolated alkaline earth clusters react with a low-pressure background of 18-crown-6 (C6) by salt abstraction exclusively. In general, the more facile abstraction from a mixed cluster produces a pair of products in which the neutral conforms to the hard-soft acid-base principle. The reactions of C6 with [MgSr(OAc)3]+ provide evidence for the existence of isomeric clusters at m/z 289. This is supported by bimodal kinetics and preliminary results of ab initio calculations.

Acetophenones in Cynanchum species, especially cynandione A and its derivatives, whose utilization and toxicity in herbal drugs and folk medicines has caused great interest in the chemical investigation, have extensive biological activities. In this paper, a facile method based on high-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (HPLC-ESI-MS(n)) was developed for the analysis of cynandione A derivatives in the roots of the Cynanchum wilfordii and C. auriculatum. ESI-MS/MS and ESI-MS(n) analysis of cynandiones A and B in negative ion mode were firstly performed employing two mass spectrometers each equipped with an ion-trap and a quadrupole time-of-flight (Q-TOF) mass analyzer. The results drawn from both instruments were similar to each other. Characteristic fragmentation pathways were proposed by comparing the spectra of two standards acquired in the experiments. The fragment ions at m/z 283 and 268 were obtained, and then were used as diagnostic ions to screen and identify cynandione A derivatives from the roots of above two species, together with an HPLC-MS(n) method. Total of 28 cynandione A derivatives comprising 4 reported and 24 novel components were identified or tentatively identified. Furthermore, breakdown curves were constructed to distinguish two types of isomers among these compounds. To our knowledge, this is the first report on characterization of acetophenones by HPLC-ESI-MS(n), which allows a rapid and complete analysis of cynandione A derivatives in roots of Cynanchum species. PMID:19201126

A large variety of phenolic compounds, including phenolic acids (hydroxybenzoic acids, hydroxycinnamic acids, and their esters), stilbenes (trans-resveratrol and trans-piceatannol), flavan-3-ols (e.g., (-)-epicatechin, (+)-catechin, and their polymers {the proanthocyanidins, PACs}), other flavonoids (e.g., isoflavones, flavanols, and flavones, etc.) and biflavonoids (e.g., morelloflavone), were identified in dry-blanched peanut skins (PS) by this study. High-performance liquid chromatography (HPLC) coupled with electrospray ionization mass spectrometry (ESI-MS(n)) was applied to separate and identify the phenolic constituents. Reversed-phase HPLC was employed to separate free phenolic compounds as well as PAC monomers, dimers, and trimers. PACs with a degree of polymerization (DP) of >4 were chromatographed via hydrophilic interaction liquid chromatography (HILIC). Tentative identification of the separated phenolics was based solely on molecular ions and MS(n) fragmentation patterns acquired by ESI-MS in the negative-ion mode. The connection sequence of PAC oligomers (DP <5) could be deduced mainly through characteristic quinone methide (QM) cleavage ions. When the DP reached 6, only a proportion of the flavan-3-ols could be ascertained in the PACs because of the extremely complicated fragmentation patterns involved. The identification of free phenolic acids, stilbenes, and flavonoids was achieved by authentic commercial standards and also by published literature data. Quantification was performed based on peak areas of the UV (free phenolic compounds) or fluorescence (PACs) signals from the HPLC chromatograms and calibration curves of commercial standards. Overall, PS contain significantly more PACs compared to free phenolic compounds. PMID:25016324

This paper reports on an accurate and rapid method to compute the onset voltage of a single or an array of electrospray emitters with complex geometries and on the correlation of the simulation with experimental data. This method permits the exact determination of the onset voltage based only on the surface tension of the sprayed liquid and on the emitter geometry. The approach starts by determining the voltage at which electrostatic forces and surface tension forces are equal for a sharpening conic surface at the tip of a capillary as a function of the apex radius of the liquid. By tracing the curve of this computed equilibrium voltage as a function of the apex radius, the onset voltage for a liquid surface with the Taylor half-angle of 49.3 deg. or larger can be determined. For smaller cone half-angles the method is only applicable to ionic sprays as an approximate knowledge of the critical field for ion emission is necessary. The combination of analytical models and finite element tools used to compute the necessary parameters is described. The method is validated on a complex microelectromechanical system emitter geometry as well as on a linear array of electrospray emitters. Finally an empirical model of the behavior of the electric field near the apex of a conic surface with asymptotes at a fixed half-angle is proposed, which allows establishing a simple method for onset voltage determination.

A facility was established that uses collected data and feeds it into mathematical models that generate improved data arrays by correcting for various losses, base line drift, and conversion to unity scaling. These developed data arrays have headers and other identifying information affixed and are subsequently stored in a Laser Materials and Characteristics data base which is accessible to various users. The two part data base: absorption - emission spectra and tabulated data, is developed around twelve laser models. The tabulated section of the data base is divided into several parts: crystalline, optical, mechanical, and thermal properties; aborption and emission spectra information; chemical name and formulas; and miscellaneous. A menu-driven, language-free graphing program will reduce and/or remove the requirement that users become competent FORTRAN programmers and the concomitant requirement that they also spend several days to a few weeks becoming conversant with the GEOGRAF library and sequence of calls and the continual refreshers of both. The work included becoming thoroughly conversant with or at least very familiar with GEOGRAF by GEOCOMP Corp. The development of the graphing program involved trial runs of the various callable library routines on dummy data in order to become familiar with actual implementation and sequencing. This was followed by trial runs with actual data base files and some additional data from current research that was not in the data base but currently needed graphs. After successful runs, with dummy and real data, using actual FORTRAN instructions steps were undertaken to develop the menu-driven language-free implementation of a program which would require the user only know how to use microcomputers. The user would simply be responding to items displayed on the video screen. To assist the user in arriving at the optimum values needed for a specific graph, a paper, and pencil check list was made available to use on the trial runs.

Electrospray is an aerosolization method that generates highly charged droplets from solutions or suspensions and, after a series of solvent evaporation -- droplet fission cycles, it results in particles carrying multiple charges. Highly charged particles are used in a variety of applications, including particle characterization, thin film deposition, nanopatterning, and inhalation studies among several others. In this work, a soft X-ray photoionization was coupled with an electrospray to obtain monodisperse, singly charged nanoparticles for applications in online size characterization with electrical mobility analysis. Photoionization with the soft X-ray charger enhanced the diffusion neutralization rate of the highly charged bacteriophages, proteins, and solid particles. The effect of nanoparticle surface charge and nanoparticle agglomeration in liquids on the electrospray process was studied experimentally and a modified expression to calculate the effective electrical conductivity of nanosuspensions was proposed. The effective electrical conductivity of TiO2 nanoparticle suspensions is strongly dependent on the electrical double layer and the agglomeration dynamics of the particles; and such dependence is more remarkable in liquids with low ionic strength. TiO2 nanoparticle agglomerates with nearly monodisperse sizes in the nanometer and submicrometer ranges were generated, by electrospraying suspensions with tuned effective electrical conductivity, and used to deposit photocatalytic films for water-splitting. Nanostructured films of iron oxide with uniform distribution of particles over the entire deposition area were formed with an electrospray system. The micro-Raman spectra of the iron oxide films showed that transverse and longitudinal optical modes are highly sensitive to the crystallize size of the electrospray-deposited films. The fabrication of films of natural light-harvesting complexes, with the aim of designing biohybrid photovoltaic devices, was

Electrospray is a commonly used ionization method for the analysis of liquids. An electrospray is a dispersed nebular of charged droplets produced under the influence of a strong electrical field. Subsequently, ions are produced in a complex process initiated by evaporation of neutral solvent molecules from these droplets. We coupled an electrospray ionization source to our previously described high resolution ion mobility spectrometer with 75mm drift tube length and a drift voltage of 5kV. When using a tritium source for chemical gas phase ionization, a resolving power of R=100 was reported for this setup. We replaced the tritium source and the field switching shutter by an electrospray needle, a desolvation region with variable length and a three-grid shutter for injecting ions into the drift region. Preliminary measurements with tetraalkylammonium halides show that the current configuration with the electrospray ionization source maintains the resolving power of R=100. In this work, we present the characterization of our setup. One major advantage of our setup is that the desolvation region can be heated separately from the drift region so that the temperature in the drift region stays at room temperature even up to desolvation region temperatures of 100°C. We perform parametric studies for the investigation of the influence of temperature on solvent evaporation with different ratios of water and methanol in the solvent for different analyte substances. Furthermore, the setup is operated in negative mode and spectra of bentazon with different solvents are presented. PMID:26838374

Femtosecond (fs) laser vaporization is used to transfer cytochrome c, myoglobin, lysozyme, and ubiquitin from the condensed phase into an electrospray (ES) plume consisting of a mixture of a supercharging reagent, m-nitrobenzyl alcohol ( m-NBA), and trifluoroacetic acid (TFA), acetic acid (AA), or formic acid (FA). Interaction of acid-sensitive proteins like cytochrome c and myoglobin with the highly charged ES droplets resulted in a shift to higher charge states in comparison with acid-stable proteins like lysozyme and ubiquitin. Laser electrospray mass spectrometry (LEMS) measurements showed an increase in both the average charge states (Zavg) and the charge state with maximum intensity (Zmode) for acid-sensitive proteins compared with conventional electrospray ionization mass spectrometry (ESI-MS) under equivalent solvent conditions. A marked increase in ion abundance of higher charge states was observed for LEMS in comparison with conventional electrospray for cytochrome c (ranging from 19+ to 21+ versus 13+ to 16+) and myoglobin (ranging from 19+ to 26+ versus 18+ to 21+) using an ES solution containing m-NBA and TFA. LEMS measurements as a function of electrospray flow rate yielded increasing charge states with decreasing flow rates for cytochrome c and myoglobin.

Electrospray ionization mass spectrometry (ESI-MS) measurements were performed under a variety of solution conditions on a highly acidic sub-fragment (B3C) of the C-terminal carbohydrate-binding repeat region of Clostridium difficile toxin B, and two mutants (B4A and B4B) containing fewer acidic residues. ESI-MS measurements performed in negative ion mode on aqueous ammonium acetate solutions of B3C at low ionic strength ( I < 80 mM) revealed evidence, based on the measured charge state distribution, of protein unfolding. In contrast, no evidence of unfolding was detected from ESI-MS measurements made in positive ion mode at low I or in either mode at higher I. The results of proton nuclear magnetic resonance and circular dichroism spectroscopy measurements and gel filtration chromatography performed on solutions of B3C under low and high I conditions suggest that the protein exists predominantly in a folded state in neutral aqueous solutions with I > 10 mM. The results of ESI-MS measurements performed on B3C in a series of solutions with high I at pH 5 to 9 rule out the possibility that the structural changes are related to ESI-induced changes in pH. It is proposed that unfolding of B3C, observed in negative mode for solutions with low I, occurs during the ESI process and arises due to Coulombic repulsion between the negatively charged residues and liquid/droplet surface charge. ESI-MS measurements performed in negative ion mode on B4A and B4B also reveal a shift to higher charge states at low I but the magnitude of the changes are smaller than observed for B3C.

A sensitive and rapid liquid chromatography/electrospray ion trap mass spectrometry (LC/MS/MS) method has been developed for the quantitative determination of medroxyprogesterone acetate (MPA) in human plasma. Plasma samples (1.0 mL) were simply extracted with pentane and the extracts were analyzed by HPLC with the detection of the analyte in the selective reaction monitoring (SRM) mode. The determination of MPA was accurate and reproducible, with a limit of quantitation of 0.05 ng/mL in plasma. The standard calibration curve for MPA was linear (r = 0.998) over the concentration range 0.05-6.0 ng/mL in human plasma. Analysis precision over the concentration range of MPA was lower than 18.8% (relative standard deviation, RSD) and accuracy was between 96.2 and 108.7%. PMID:11675672

Silica microballs have a wide range of applications in the field of optics, electronics, biotechnology chemical industry, and so on. In this work, a new approach, electrospraying, was used to coat the silica microballs onto the glass substrate, and the coating results were compared to spin-coating and dip-coating. Good microball size control could be achieved using the electrospraying method. X-Ray Diffraction (XRD) results showed that amorphous silica microballs were obtained. From Scanning Electron Microscopy (SEM) images, we can see that uniform microball size was achieved. In general, the results are better than what can be achieved by spin-coating, and comparable to that of dip-coating. However, electrospraying has great potential in mass production, especially for large-area fabrication.

Systems and methods that provide up to complete transmission of ions between coupled stages with low effective ion losses. An "interfaceless" electrospray ionization system is further described that operates an electrospray at a reduced pressure such that standard electrospray sample solutions can be directly sprayed into an electrodynamic ion funnel which provides ion focusing and transmission of ions into a mass analyzer. Furthermore, chambers maintained at different pressures can allow for more optimal operating conditions for an electrospray emitter and an ion guide.

It is known that the cochlear microphonic voltage exhibits much broader tuning than does the basilar membrane motion. The most commonly used explanation for this is that when an electrode is inserted at a particular point inside the scala media, the microphonic potentials of neighbouring hair cells have different phases, leading to cancelation at the electrodes location. In situ recording of functioning outer hair cells (OHCs) for investigating this hypothesis is exceptionally difficult. Therefore, to investigate the discrepancy between the tuning curves of the basilar membrane and those of the cochlear microphonic, and the effect of phase cancellation of adjacent hair cells on the broadness of the cochlear microphonic tuning curves, we use an electromechanical model of the cochlea to devise an experiment. We explore the effect of adjacent hair cells (i.e., longitudinal phase cancellation) on the broadness of the cochlear microphonic tuning curves in different locations. The results of the experiment indicate that active longitudinal coupling (i.e., coupling with active adjacent outer hair cells) only slightly changes the broadness of the CM tuning curves. The results also demonstrate that there is a π phase difference between the potentials produced by the hair bundle and the soma near the place associated with the characteristic frequency based on place-frequency maps (i.e., the best place). We suggest that the transversal phase cancellation (caused by the phase difference between the hair bundle and the soma) plays a far more important role than longitudinal phase cancellation in the broadness of the cochlear microphonic tuning curves. Moreover, by increasing the modelled longitudinal resistance resulting the cochlear microphonic curves exhibiting sharper tuning. The results of the simulations suggest that the passive network of the organ of Corti determines the phase difference between the hair bundle and soma, and hence determines the sharpness of the

In various embodiments, a device may generally comprise a capillary having a first end and a second end; a laser to emit energy at a sample in the capillary to ablate the sample and generate an ablation plume in the capillary; an electrospray apparatus to generate an electrospray plume to intercept the ablation plume to produce ions; and a mass spectrometer having an ion transfer inlet to capture the ions. The ablation plume may comprise a collimated ablation plume. The device may comprise a flow cytometer. Methods of making and using the same are also described.

In various embodiments, a device may generally comprise a capillary having a first end and a second end; a laser to emit energy at a sample in the capillary to ablate the sample and generate an ablation plume in the capillary; an electrospray apparatus to generate an electrospray plume to intercept the ablation plume to produce ions; and a mass spectrometer having an ion transfer inlet to capture the ions. The ablation plume may comprise a collimated ablation plume. The device may comprise a flow cytometer. Methods of making and using the same are also described.

Multiplexed electrospray deposition device capable of delivering picoliter volumes made by silicon micromachining technology has been developed as a deposition tool for making protein microarrays in a noncontact mode. Upon application of potential difference in the range of 7-9kV, biomolecules dissolved in suitable buffer with nonionic surfactant and loaded on the electrospray tips were dispensed on the substrate with microfabricated hydrogel features (1-10μm) in cone-jet mode. Schiff base chemistry followed by reductive amination was utilized for covalent immobilization.

We report for the first time a novel erythrocyte-like graphene microsphere (ELGMs) which can be produced with high quality and mass production capability via electrospray assisted self-assembly. Through simple electrospray treatment of GO suspension into coagulation bath followed by chemical reduction, large quantity of ELGMs with uniform morphology and size can be obtained with production rate of around 2.4 mg/h. Compared with other 3D structures, the ELGMs have a very interesting structural characteristic of perfect exterior doughnut shape and interior porous network. Accordingly, the as-prepared porous ELGMs exhibit excellent capability for fast and recyclable removal of oil and toxic organic solvents from water, reaching up to 216 times of its weight in absorption efficiency, which is tens of times higher than that of conventional sorbent materials. It is strongly believed that the novel hierarchical graphene structures and synergy among different techniques will lead to more future advances in graphene applications.

The ability of electrospray to encapsulate the bioactive compound extracted from Jasmine flower with β-Cyclodextrion (β-CD) without any thermal-assisted processing was demonstrated in this study. The extraction of Jasmine compound were conducted using sonicator at 70 000 Hz, for 10 minutes and followed by mixing of the filtered compound with β-CD. Then, the mixture was electrosprayed under a stable Taylor cone jet mode at the voltage of 4 - 5 kV, with flow rate of 0.2 ml/hour. The aluminum substrate that used for collecting the deposit was placed at 30 cm from the needle's tip to allow the occurrence of evaporation and droplet fission until the droplet transform to solid particles. Characteristics of solidified bioactive compound from Jasmine flower (non-encapsulated compound) and solidified bioactive compound with β-CD (encapsulated compound) were studied in this work. From SEM images, it can be observed that the particles size distribution of encapsulated compound deposits have better deposition array and did not aggregate with each other compared to the non-encapsulated compound. FE-SEM images of encapsulated compound deposits indicate more solid crystal looks while non-encapsulated compound was obtained in the porous form. The electrospray process in this work has successfully encapsulated the Jasmine compound with β-CD without any thermal-assisted process. The encapsulation occurrence was determined using FTIR analysis. Identical peaks that referred to the β-CD were found on the encapsulated compound demonstrated that most deposits were encapsulated with β-CD.

Electrospray ionization (ESI) is a soft ionization technique that allows transfer of fragile biomolecules directly from solution into the gas phase. An instrumental analysis laboratory experiment is designed that would introduce the students to the ESI technique, major parameters of the ion trap mass spectrometers and some caveats in…

Desorption electrospray ionization-mass spectrometry (DESI-MS) was evaluated for the detection of proteins ranging in molecular mass from 12 to 66 kDa. Proteins were uniformly deposited on a solid surface without pretreatment and analyzed with a DESI source coupled to a quadrupole ion trap mass spec...

The electrospray-deposited patterns of graphene onto filter paper were characterized to study the effect of cellulose acetate phthalate (CAP) binder on the surface resistance of the resulting paper. The amount of CAP determines the extent of penetration of graphene into the heterogeneous networks, because graphene gets anchored and crowded into the network with CAP. A graphene-dispersed ink was prepared in water using sodium dodecylbenzenesulfonate, and this ink was used to fabricate graphene-coated paper (GCP) by electrospray deposition technique. The SEM images of the GCP revealed the impregnation of graphene into the filter paper. The mechanical properties and surface resistance of the GCP were studied using a universal testing machine (UTM) and indigenous four-probe meter, respectively. The low-cost GCP prepared in this study showed relatively low surface resistance (96.2 omega/sq) owing to the effective electro-conducting pathway provided by the crowded and impregnated deposition of grapheme onto the filter paper. Consequently, CAP improved the electrical and mechanical characteristics of GCP, even though only a small amount of graphene was used during deposition. PMID:24245203

Molecular weight distributions of fulvic acid from the Suwannee River, Georgia, were investigated by electrospray ionization/quadrupole mass spectrometry (ESI/QMS), and fragmentation pathways of specific fulvic acid masses were investigated by electrospray ionization/ion trap multistage tandem mass spectrometry (ESI/MST/MS). ESI/QMS studies of the free acid form of low molecular weight poly(carboxylic acid) standards in 75% methanol/25% water mobile phase found that negative ion detection gave the optimum generation of parent ions that can be used for molecular weight determinations. However, experiments with poly(acrylic acid) mixtures and specific high molecular weight standards found multiply charged negative ions that gave a low bias to molecular mass distributions. The number of negative charges on a molecule is dependent on the distance between charges. ESI/MST/MS of model compounds found characteristic water loss from alcohol dehydration and anhydride formation, as well as CO2 loss from decarboxylation, and CO loss from ester structures. Application of these fragmentation pathways to specific masses of fulvic acid isolated and fragmented by ESI/MST/MS is indicative of specific structures that can serve as a basis for future structural confirmation after these hypothesized structures are synthesized.

A sensitive approach, based on semi-quantitative measurement of the characteristic fragments in multi-stage extractive electrospray ionization mass spectrometry (EESI-MS(n)), was developed for fast detection of trace levels of lead in aqueous liquids including mineral water, lake water, tap water, energy drinks, soft drinks, beer, orange juice, and tea. A disodium ethylene-diamine-tetraacetic acid (EDTA) aqueous solution was electrosprayed to produce negatively charged primary ions which then intersected the neutral sample plume to generate anions of EDTA-Pb(II) complexes. The charged EDTA-Pb(II) complexes were characterized with multistage collision induced dissociation (CID) experiments. The limit of detection (LOD) using EESI-MS(3) was estimated to be at the level of 10(-13)g/mL for directly detecting lead in many of these samples. The linear dynamic range was higher than 2 orders of magnitude. A single sample analysis could be completed within 2 min with reasonable semi-quantitative performance, e.g., relative standard deviations (RSDs) for deionized water were 4.6-7.6% during 5 experimental runs (each of them had 10 repeated measurements). Coca-cola and Huiyuan orange juice, representative beverage samples with complex matrices, generated recovery rates of 91.5% and 129%, respectively. Our experimental data demonstrated that EESI-MS is a useful tool for the fast detection of lead in various solutions, and EESI-MS showed promises for fast screening of lead-contaminated aqueous liquid samples. PMID:22939131

We report on the development of a time-of-flight (ToF) mass spectrometer with a highly efficient electrostatic ion guide for enhancing detectability in ToF mass spectrometry. This 65-cm long ion guide consists of 13 cascaded stages of Einzel lens to collect a large fraction of emitted charges over a wide emission angle and energy spread for time-of-flight measurements. Simulations show that the ion guide can collect 100% of the charges with up to 23° emission half-angle or 30% energy spread irrespective of their specific charge. We demonstrate this ion guide as applied to electrospray ion sources. Experiments performed with tungsten needle electrospraying the ionic liquid EMI-BF4 showed that up to 80% of the emitted charges could be collected at the end of the flight tube. Flight times of monomers and dimers emitted from the needles were measured in both positive and negative emission polarities. The setup was also used to characterize the electrospray from microfabricated silicon capillary emitters and nearly 30% charges could be collected even from a 40(°) emission half-angle. This setup can thus increase the fraction of charge collection for ToF measurement and spray characteristics can be obtained from a very large fraction of the emission in real time. PMID:24833357

We report on the development of a time-of-flight (ToF) mass spectrometer with a highly efficient electrostatic ion guide for enhancing detectability in ToF mass spectrometry. This 65-cm long ion guide consists of 13 cascaded stages of Einzel lens to collect a large fraction of emitted charges over a wide emission angle and energy spread for time-of-flight measurements. Simulations show that the ion guide can collect 100% of the charges with up to 23° emission half-angle or 30% energy spread irrespective of their specific charge. We demonstrate this ion guide as applied to electrospray ion sources. Experiments performed with tungsten needle electrospraying the ionic liquid EMI-BF4 showed that up to 80% of the emitted charges could be collected at the end of the flight tube. Flight times of monomers and dimers emitted from the needles were measured in both positive and negative emission polarities. The setup was also used to characterize the electrospray from microfabricated silicon capillary emitters and nearly 30% charges could be collected even from a 40° emission half-angle. This setup can thus increase the fraction of charge collection for ToF measurement and spray characteristics can be obtained from a very large fraction of the emission in real time.

Horizontally curved bridges meet an increasing demand for complex highway geometries in congested urban areas. A popular type of curved bridge consists of steel I-girders interconnected by cross-frames and a composite concrete deck slab. Prior to hardening of the concrete deck each I-girder is susceptible to a lateral torsional buckling-type failure. Unlike a straight I-girder, a curved I-girder resists major components of stress resulting from strong axis bending, weak axis bending and warping. The combination of these stresses reduce the available strength of a curved girder versus that of an equivalent straight girder. Experiments demonstrating the ultimate strength characteristics of curved girders are few in number. Of the available experimental research, few studies have used full scale-tests and boundary conditions indicative of those found in an actual bridge structure. Unlike straight girders, curved girders are characterized by nonlinear out-of-plane deformations which, depending upon the magnitude of curvature, may occur at very low load levels. Because of the inherent nonlinear behaviour, some have questioned the application of the term lateral torsional buckling to curved girders; rather curved girders behave in a manner consistent with a deflection-amplification problem. Even with the advent of sophisticated analytical techniques, there is a glaring void in the documented literature regarding calibration of these techniques with known experimental curved girder behaviour. Presented here is an analytical study of the nonlinear modelling of curved steel girders and bridges. This is accomplished by incorporating large deflection and nonlinear material behaviour into three dimensional finite element models generated using the program ANSYS. Emphasis is placed on the calibration of the finite method with known experimental ultimate strength data. It is demonstrated that accurate predictions of load deformation and ultimate strength are attainable via the

Desorption electrospray ionization mass spectrometry was investigated as a means to qualitatively identify and to quantify analytes directly from developed normal-phase thin layer chromatography plates. The atmospheric sampling capillary of a commercial ion trap mass spectrometer was extended to permit sampling and ionization of analytes in bands separated on intact TLC plates (up to 10 cm x 10 cm). A surface positioning software package and the appropriate hardware enabled computer-controlled surface scanning along the length of development lanes or at fixed RF value across the plates versus the stationary desorption electrospray emitter. Goldenseal (Hydrastis canadensis) and related alkaloids and commercial dietary supplements were used as standards and samples. Alkaloid standards and samples were spotted and separated on aluminum- or glass-backed plates using established literature methods. The mass spectral signal levels as a function of desorption spray solvent were investigated with acetonitrile proving superior to methanol. The detection levels (ca. 5 ng each or 14 -28 pmol) in mass spectral full scan mode were determined statistically from the calibration curves (2.5 - 100 pmol) for the standards berberine, palmatine and hydrastinine spotted as a mixture and separated on the plates. Qualitative screening of the major alkaloids present in six different over-the-counter "goldenseal" dietary supplements was accomplished by obtaining full scan mass spectra during surface scans along the development lane in the direction of increasing RF value. In one sample, alkaloids were detected that strongly suggested the presence of at least one additional herb undeclared on the product label. These same data indicated the misidentification of one of the alkaloids in the TLC literature. Quantities of the alkaloids present in two of the samples determined using the mass spectral data were in reasonable agreement with the label values indicating the quantitative ability of

The equilibrium of a flexible inextensible string, or chain, in the centrifugal force field of a rotating reference frame is investigated. It is assumed that the end points are fixed on the rotation axis. The shape of the curve, the skipping rope curve or "troposkien", is given by the Jacobi elliptic function sn. (Contains 3 figures.)

An experiment published in this "Journal" has been revisited and it is found that the curve pattern of the anodic polarization curve for iron repeats itself successively when the potential scan is repeated. It is surprising that this observation has not been reported previously in the literature because it immediately brings into…

Prior work with electrosprays in vacuum of mixtures of ionic liquids (ILs) and the moderately high boiling point (T{sub b}) solvents formamide (FM) and propylene carbonate (PC) (T{sub b} of 210 and 241 °C) has shown that the charged drops produced have reasonably narrow charge/mass distributions, controllable over a wide mass/charge range. This enables their use as propellants in electrical propulsion with specific impulse I{sub sp} varying from a few hundred to a few thousand seconds (10 kV beam energy) and with excellent propulsion efficiency. However, some limitations are imposed by the finite room temperature volatility of FM and PC. Here, we seek improved performance from propellants based on the polar but viscous solvent Sulfolane (SF; ε = 43.2, μ = 10.3 cP) and the low viscosity but less polar solvent tributyl phosphate (TBP; ε = 8.9, μ = 3.4 cP), both with T{sub b} > 280 °C. Neither TBP nor its low viscosity mixtures with SF achieve the electrical conductivities needed to yield high I{sub sp}. Most ILs used in SF/IL mixtures tested were based on the 1-ethyl-3-methylimidazolium (EMI) or 1,3-dimethylimidazolium (DMI) cations, including EMI-BF{sub 4}, EMI-N(CN){sub 2}, and DMI-N(CN){sub 2}. These combinations reach high conductivities, some approaching 3 S/m, but have limited propulsive performance because evaporation of ions directly from the electrified meniscus produces undesirable mixed beams of drops and ions. Exceptional characteristics are found in mixtures of SF with ethylammonium nitrate (EAN), where the small EA{sup +} cation is strongly bound to the solvent, greatly delaying ion evaporation from the meniscus. Evidence on the formation of nano-jets with diameters as small as 1 nm is seen. Although unprecedented, this finding agrees with what would be expected if ion evaporation were suppressed. SF/EAN mixtures thus provide the best available sources to produce the smallest possible nanodrops, minimally polluted by

Prior work with electrosprays in vacuum of mixtures of ionic liquids (ILs) and the moderately high boiling point (Tb) solvents formamide (FM) and propylene carbonate (PC) (Tb of 210 and 241 °C) has shown that the charged drops produced have reasonably narrow charge/mass distributions, controllable over a wide mass/charge range. This enables their use as propellants in electrical propulsion with specific impulse Isp varying from a few hundred to a few thousand seconds (10 kV beam energy) and with excellent propulsion efficiency. However, some limitations are imposed by the finite room temperature volatility of FM and PC. Here, we seek improved performance from propellants based on the polar but viscous solvent Sulfolane (SF; ɛ = 43.2, μ = 10.3 cP) and the low viscosity but less polar solvent tributyl phosphate (TBP; ɛ = 8.9, μ = 3.4 cP), both with Tb > 280 °C. Neither TBP nor its low viscosity mixtures with SF achieve the electrical conductivities needed to yield high Isp. Most ILs used in SF/IL mixtures tested were based on the 1-ethyl-3-methylimidazolium (EMI) or 1,3-dimethylimidazolium (DMI) cations, including EMI-BF4, EMI-N(CN)2, and DMI-N(CN)2. These combinations reach high conductivities, some approaching 3 S/m, but have limited propulsive performance because evaporation of ions directly from the electrified meniscus produces undesirable mixed beams of drops and ions. Exceptional characteristics are found in mixtures of SF with ethylammonium nitrate (EAN), where the small EA+ cation is strongly bound to the solvent, greatly delaying ion evaporation from the meniscus. Evidence on the formation of nano-jets with diameters as small as 1 nm is seen. Although unprecedented, this finding agrees with what would be expected if ion evaporation were suppressed. SF/EAN mixtures thus provide the best available sources to produce the smallest possible nanodrops, minimally polluted by ions.

Characteristic sludge ecosystems arising in anaerobic membrane bioreactors of three pilot-scale plants treating low-strength (less than 1 g of biological oxygen demand per liter) sewage or soybean-processing wastewater were examined by analysis of the colony-forming-curves (CFC) obtained by counting colonies at suitable intervals. The wastewaters, containing high amounts of suspended solids (SS) (SS/chemical oxygen demand ratio, 0.51 to 0.80), were treated by using two types of bioreactors: (i) a hydrolyzation reactor for solubilization and acidification of SS in wastewater and (ii) a methane fermentation reactor for producing methane. The colony counts for the two sewage treatment plants continued to increase even after 3 weeks of incubation, whereas those for soybean-processing wastewater reached an approximately constant level within 3 weeks of incubation. The CFCs were analyzed by correlating the rate of colony appearance on roll tubes with the physiological types of bacteria present in the bioreactors. It was found that there were large numbers of slow-colony-forming anaerobic bacteria within the bioreactors and that the viable populations consisted of a few groups with different growth rates. It is considered that the slow-growing colonies appearing after 10 days of incubation were the dominant microflora in the sewage treated by hydrolyzation reactors. In particular, highly concentrated sludge (30.0 g of mixed-liquor volatile SS per liter) retained by the membrane separation module contained a large number of such bacteria. Slow-growing colonies of these bacteria could be counted by using a sludge extract medium prepared from only the supernatant of autoclaved sludge. In addition, the highest colony counts were almost always obtained with the sludge extract medium, meaning that most of the anaerobic bacteria in these sludges have complex nutrient requirements for growth. This report also indicates the usefulness of application of the CFC analysis method to

The scanning mass spectrometry (SMS) probe is a new electrospray ion source. Motivated by the need for untargeted chemical imaging of dynamic events in solution, we have exploited an approach to electrospray ionization (ESI) that allows continuous sampling from a highly localized volume (approximately picoliters) in a liquid environment, softly ionizes molecules in the sample to render them amenable for mass spectrometric analysis, and sends the ions to the mass spectrometer. The key underlying concepts for our approach are (1) treating the electrospray capillary inlet as a chemical scanning probe and (2) locating the electrospray point as close as possible to the sampling point, thus providing the shortest response time possible. This approach enables chemical monitoring or imaging of submerged interfaces, providing access to details of spatial heterogeneity and temporal changes within liquid samples. It also permits direct access to liquid/ liquid interfaces for ESI-MS analysis. In this letter we report the first demonstrations of these capabilities of the SMS probe and describe some of the probe's basic characteristics. PMID:19904914

We report here the development of a corona discharge (CD) initiated electrochemical (EC) electrospray ionization (ESI) technique using a standard electrospray ion source. This is a new ionization technique distinct from ESI, electrochemistry inherent to ESI, APCI, and techniques using hydroxyl radicals produced under atmospheric pressure conditions. By maximizing the observable CD at the tip of a stainless steel ESI capillary, efficient electrochemical oxidation of electrochemically active compounds is observed. For electrochemical oxidation to be observed, the ionization potential of the analyte must be lower than Fe. Ferrocene labeled compounds were chosen as the electrochemically active moiety. The electrochemical cell in the ESI source was robust, and generated ions with selectivity according to the ionization potential of the analytes and up to zeptomolar sensitivity. Our results indicate that CD initiated electrochemical ionization has the potential to become a powerful technique to increase the dynamic range, sensitivity, and selectivity of ESI experiments. PMID:19747843

Micro- and nanotechnology are tools being used strongly in the area of food technology. The electrospray technique is booming because of its importance in developing micro- and nanoparticles containing an active ingredient as bioactive compounds, enhancing molecules of flavors, odors, and packaging coatings, and developing polymers that are obtained from food (proteins, carbohydrates), as chitosan, alginate, gelatin, agar, starch, or gluten. The electrospray technique compared to conventional techniques such as nanoprecipitation, emulsion-diffusion, double-emulsification, and layer by layer provides greater advantages to develop micro- and nanoparticles because it is simple, low cost, uses a low amount of solvents, and products are obtained in one step. This technique could also be applied in the agrifood sector for the preparation of controlled and/or prolonged release systems of fertilizer or agrochemicals, for which more research must be conducted. PMID:25938374

Inulin, a naturally occurring polysaccharide, was acetylated to make it processable by electrospraying, a facile and single step method for microparticle fabrication. Electrospraying process parameters were optimized for fabrication of spherical and monodisperse indomethacin (IDM) loaded inulin acetate (INA) microparticles. The apparent entrapment efficiency of IDM was determined to be 100%, whereas working encapsulation efficiency was estimated to be 35.39 ± 1.63%. Differential scanning calorimetry and X-ray diffraction analysis confirmed molecular dispersion of IDM in an amorphous state within the INA matrix. Finally, the results from in vitro release study performed in simulated gastro-intestinal fluids demonstrated that IDM was released only in simulated colonic fluid that contained inulinase. Therefore, this study demonstrates that acetylation of inulin does not alter its susceptibility to inulinase and that microparticles fabricated from INA can be developed as a colon targeting drug delivery system. PMID:25129739

To overcome the limitations of the conventional encapsulation methods and improve the potential use of the electrospray method as a drug delivery system, an electrospray system using a triple coaxial nozzle was developed to generate multishell capsules. Two conducting fluids, ethylene glycol and 4-hydroxybutyl acrylate, and one nonconducting fluid, olive oil, were chosen to manufacture the multishell capsules. The capsules were solidified by a photopolymerization device. We investigated the size distributions and visualized the capsules changing fluid flow rates. Dispersive Raman spectra were also monitored to determine the chemical composition of the capsules. The multishell capsules were generated in the overlapped cone-jet mode regime of the conducting fluids, and the sizes and shell thicknesses were controlled by the flow rates and applied voltages. PMID:20459114

An automated electrospray based sampling system and method for analysis obtains samples from surface array spots having analytes. The system includes at least one probe, the probe including an inlet for flowing at least one eluting solvent to respective ones of a plurality of spots and an outlet for directing the analyte away from the spots. An automatic positioning system is provided for translating the probe relative to the spots to permit sampling of any spot. An electrospray ion source having an input fluidicly connected to the probe receives the analyte and generates ions from the analyte. The ion source provides the generated ions to a structure for analysis to identify the analyte, preferably being a mass spectrometer. The probe can be a surface contact probe, where the probe forms an enclosing seal along the periphery of the array spot surface.

Despite an almost two thousand year history, origami, the art of folding paper, remains a challenge both artistically and scientifically. Traditionally, origami is practiced by folding along straight creases. A whole new set of shapes can be explored, however, if, instead of straight creases, one folds along arbitrary curves. We present a mechanical model for curved fold origami in which the energy of a plastically-deformed crease is balanced by the bending energy of developable regions on either side of the crease. Though geometry requires that a sheet buckle when folded along a closed curve, its shape depends on the elasticity of the sheet. NSF DMR-0846582.

We have developed an electrospraying technique inspired from Marangoni flow seen in nature. We demonstrate our ability to synthesise highly crystalline uniform perovskite thin films with enhanced coverage and high absorption. Due to a difference in the vapour pressure of DMSO and NMP, a gradient force is developed that helps in propagating the incoming precursor droplet to coalesce and merge with other droplets thus inducing a dynamic self-assembly within the thin film. This results in thin films with high uniformity and good morphological and topological characteristics, that collectivelty resulted in a respectable PCE of greater than 14%. Optical studies are conducted in parallel to better understand the energy phase space of perovskite crystals. The high temperature tetragonal phase showed a high recombination rate of 180 ns, ideal for photovoltaic performances, while the low temperature measurements reveal considerable complexity in spectral and dynamic properties that demand further invesgtiation.

We report the use of silver nanoparticles to obtain surface-enhanced Raman spectra of Crystal Violet in an electrospray plume. Surface enhancement allowed detection at low concentrations with the high specificity afforded by vibrational spectroscopy. SERS spectra were used to obtain an axial concentration profile closely matching that obtained in previous fluorescence experiments. SERS can provide more analyte structural information than has been obtainable from fluorescence studies of the plume. PMID:16351168

This dissertation presents a new method of producing nearly monodisperse electrospray using charged capillary standing waves. This method, based on the Ultrasonically Aided Electrospraying (UAE) technology concept invented by the author, includes the steps of dispensing a liquid on the top surface of a diaphragm so as to form a liquid film on the surface of the diaphragm, setting the diaphragm into vibration using piezoelectric transducers so as to induce capillary standing waves in the liquid film, applying electric charge to the capillary standing waves so that electrospray is extracted from the crests of the capillary standing waves. Theoretical analysis on the formation of charged particles from charged capillary standing waves at critically stable condition is performed. An experimental UAE system is designed, built, and tested and the performance of this new technology concept is assessed. Experimental results validate the capabilities of the UAE concept. The method has several applications including electric space propulsion, nano particulate technologies, nanoparticle spray coating and painting techniques, semiconductor fabrication and biomedical processes. Two example applications in electric space propulsion and nanoparticle spray coating are introduced.

Uses LOGO to enhance the applicability of curve stitching in the mathematics curriculum. Presents the formulas and computer programs for the construction of parabolas, concentric circles, and epicycloids. Diagrams of constructed figures are provided. (MDH)

Characterizing and elucidating structures is a commonplace and necessary activity in the pharmaceutical industry with mass spectrometry and NMR being the primary tools for analysis. Although many functional groups are readily identifiable, quaternary ammonium cations have proven to be difficult to unequivocally identify using these techniques. Due to the lack of an N-H bond, quaternary ammonium groups can only be detected in the 1H NMR spectra by weak signals generated from long-range 14N-H coupling, which by themselves are inconclusive evidence of a quaternary ammonium functional group. Due to their low intensity, these signals are frequently not detected. Additionally, ions cannot be differentiated in a mass spectrum as an M+ or [M + H]+ ion without prior knowledge of the compound's structure. In order to utilize mass spectrometry as a tool for determining this functionality, ion cluster formation of quaternary ammonium cations and non-quaternary amines was studied using electrospray ionization. Several mobile phase modifiers were compared; however, the addition of small amounts of trifluoroacetic acid proved superior in producing characteristic and intense [M +2TFA]- clusters for compounds containing quaternary ammonium cations when using negative electrospray. By fragmenting this characteristic ion using CID, nearly all compounds studied could be unambiguously identified as containing a quaternary ammonium cation or a non-quaternary amine attributable to the presence (non-quaternary amine) or absence (quaternary ammonium cation) of the resulting [2TFA + H]- ion in the product spectra. This method of analysis provides a rapid, novel, and reliable technique for indicating the presence of quaternary ammonium cations in order to aid in structural elucidation.

that drivers behave differently depending on the curve direction where both speed and acceleration were higher on right than left curves. The implication of this study is that curve direction should be taken into consideration to a greater extent when designing and redesigning curves. It appears that the driver and the vehicle are influenced by different infrastructure factors depending on the curve direction. In addition, the results suggest that the vehicle dynamics response alone cannot explain the higher crash risk in right curves. Further studies of the links between driver, vehicle, and highway characteristics are needed, such as naturalistic driving studies, to identify the key safety indicators for highway safety. PMID:21050608

An inlet for a gas turbine engine was disposed about a curved centerline for the purpose of accepting intake air that is flowing at an angle to engine centerline and progressively turning that intake airflow along a curved path into alignment with the engine. This curved inlet is intended for use in under the wing locations and similar regions where airflow direction is altered by aerodynamic characteristics of the airplane. By curving the inlet, aerodynamic loss and acoustic generation and emission are decreased.

A system and method are disclosed that provide up to complete transmission of ions between coupled stages with low effective ion losses. A novel "interfaceless" electrospray ionization system is further described that operates the electrospray at a reduced pressure such that standard electrospray sample solutions can be directly sprayed into an electrodynamic ion funnel which provides ion focusing and transmission of ions into a mass analyzer.

The performance of several electrospray ionization emitters with different orifice inside diameters (i.d.s), geometries, and materials are compared. The sample solution is delivered by pressure driven flow, and the electrospray ionization voltage and flow rate are varied systematically for each emitter investigated, while the signal intensity of a standard is measured. The emitters investigated include a series of emitters with a tapered outside diameters (o.d.) and unaltered i.d.s, a series of emitters with tapered o.d.s and i.d.s, an emitter with a monolithic frit and a tapered o.d., and an emitter fabricated from polypropylene. The results show that for the externally etched emitters, signal was nearly independent of i.d. and better ion utilization was achieved at lower flow rates. Furthermore, emitters with a 50 μm i.d. and an etched o.d. produced about 1.5 times more signal than etched emitters with smaller i.d.s and about 3.5 times more signal than emitters with tapered inner and outer dimensions. Additionally, the work presented here has important implications for applications in which maximizing signal intensity and reducing frictional resistance to flow are necessary. Overall, the work provides an initial assessment of the critical parameters that contribute to maximizing the signal for electrospray ionization sources interfaced with pressure driven flows. PMID:21989703

The performance of several electrospray ionization emitters with different orifice inside diameters (i.d.s), geometries, and materials are compared. The sample solution is delivered by pressure driven flow, and the electrospray ionization voltage and flow rate are varied systematically for each emitter investigated, while the signal intensity of a standard is measured. The emitters investigated include a series of emitters with a tapered outside diameters (o.d.) and unaltered i.d.s, a series of emitters with tapered o.d.s and i.d.s, an emitter with a monolithic frit and a tapered o.d., and an emitter fabricated from polypropylene. The results show that for the externally etched emitters, signal was nearly independent of i.d. and better ion utilization was achieved at lower flow rates. Furthermore, emitters with a 50 μm i.d. and an etched o.d. produced about 1.5 times more signal than etched emitters with smaller i.d.s and about 3.5 times more signal than emitters with tapered inner and outer dimensions. Additionally, the work presented here has important implications for applications in which maximizing signal intensity and reducing frictional resistance to flow are necessary. Overall, the work provides an initial assessment of the critical parameters that contribute to maximizing the signal for electrospray ionization sources interfaced with pressure driven flows.

Changes in liquid composition during gradient elution liquid chromatography (LC) and mass spectrometry (MS) analyses affect the electrospray operation. To establish methodologies for judicious selection of the electrospray voltage, we monitored in real-time the effect of the LC gradient on the spray current. The optimum range of the electrospray voltage shifted to lower values as the concentration of organic solvent in the eluent increased during reversed-phase LC analyses. These results provided the means to rationally select the voltage that ensured successful electrospray operation throughout gradient elution LC-MS experiments. A small run-to-run drift in the spray current was observed for electrosprays operated at constant voltage. This could be the result of fouling or degradation of the electrospray emitter, which affected the electric field driving the electrospray. Algorithms using feedback from spray current measurements to maintain the electrospray voltage within the optimum operating range throughout gradient elution LC-MS were evaluated. The electrospray operation with voltage regulation and at constant, judiciously selected voltage during gradient elution LC-MS measurements produced data with similar reproducibility.

Recently a number of techniques have combined laser ablation with liquid capture for mass spectrometry spot sampling and imaging applications. The newly developed non-contact liquid-vortex capture probe has been used to efficiently collect 355 nm UV laser ablated material in a continuous flow solvent stream in which the captured material dissolves and then undergoes electrospray ionization. This sampling and ionization approach has produced what appear to be classic electrospray ionization spectra; however, the softness of this sampling/ionization process versus simple electrospray ionization has not been definitely determined. A series of benzlypyridinium salts, known as thermometer ions, were used to comparemore » internal energy distributions between electrospray ionization and the UV laser ablation liquid-vortex capture probe electrospray combination. Measured internal energy distributions were identical between the two techniques, even with differences in laser fluence (0.7-3.1 J cm-2) and when using UV-absorbing or non-UV-absorbing sample substrates. This data indicates ions formed directly by UV laser ablation, if any, are likely an extremely small constituent of the total ion signal observed. Instead, neutral molecules, clusters or particulates ejected from the surface during laser ablation, subsequently captured and dissolved in the flowing solvent stream then electrosprayed are the predominant source of ion signal observed. The electrospray ionization process used controls the softness of the technique.« less

Recently a number of techniques have combined laser ablation with liquid capture for mass spectrometry spot sampling and imaging applications. The newly developed non-contact liquid-vortex capture probe has been used to efficiently collect 355 nm UV laser ablated material in a continuous flow solvent stream in which the captured material dissolves and then undergoes electrospray ionization. This sampling and ionization approach has produced what appear to be classic electrospray ionization spectra; however, the softness of this sampling/ionization process versus simple electrospray ionization has not been definitely determined. A series of benzlypyridinium salts, known as thermometer ions, were used to compare internal energy distributions between electrospray ionization and the UV laser ablation liquid-vortex capture probe electrospray combination. Measured internal energy distributions were identical between the two techniques, even with differences in laser fluence (0.7-3.1 J cm-2) and when using UV-absorbing or non-UV-absorbing sample substrates. This data indicates ions formed directly by UV laser ablation, if any, are likely an extremely small constituent of the total ion signal observed. Instead, neutral molecules, clusters or particulates ejected from the surface during laser ablation, subsequently captured and dissolved in the flowing solvent stream then electrosprayed are the predominant source of ion signal observed. The electrospray ionization process used controls the softness of the technique.

Electrospray-assisted laser desorption/ionization (ELDI), an ionization method that combines laser desorption and electrospray ionization (ESI), can be used under ambient conditions to characterize organic compounds (including FD&C dyes, amines, extracts of a drug tablet) separated in the central track on a thin-layer chromatography (TLC) plate coated with either reversed-phase C18 particles or normal-phase silica gel. After drying, the TLC plate was placed on an acrylic sample holder set in front of the sampling skimmer of an ion trap mass analyzer. The chemicals at the center of the TLC plate were analyzed by pushing the sample holder into the path of a laser beam with a syringe pump. The molecules in the sample spot were desorbed by continuously irradiating the surface of the TLC plate with a pulsed nitrogen laser. Then, the desorbed sample molecules entered an ESI plume where they were ionized through the reactions with the charged species (including protons, hydronium ions and their cluster ions, solvent ions, and charged droplets) generated by electrospraying a methanol/water solution. MS/MS analyses were also performed to further characterize the analytes. The detection limit of TLC/ELDI/MS is approximately 10(-6) M. This was evaluated by using FD&C red dye as the standard. A linear relationship was found for the calibration curve with the concentration of FD&C red dye ranged from 10(-3) to 10(-6) M. PMID:17929897

IGMtransmission is a Java graphical user interface that implements Monte Carlo simulations to compute the corrections to colors of high-redshift galaxies due to intergalactic attenuation based on current models of the Intergalactic Medium. The effects of absorption due to neutral hydrogen are considered, with particular attention to the stochastic effects of Lyman Limit Systems. Attenuation curves are produced, as well as colors for a wide range of filter responses and model galaxy spectra. Photometric filters are included for the Hubble Space Telescope, the Keck telescope, the Mt. Palomar 200-inch, the SUBARU telescope and UKIRT; alternative filter response curves and spectra may be readily uploaded.

We investigate the Rayleigh discharge and evaporation dynamics of highly charged two-component droplets consisting principally of methanol with 2-methoxyethanol, tert-butanol, or m-nitrobenzyl alcohol. A phase Doppler anemometer (PDA) characterizes droplets generated by electrospray ionization (ESI) according to size, velocity, and charge as they move through a uniform electric field within an ion mobility spectrometer (IMS). Repeated field reversals result in droplet "ping-pong" through the PDA. This generates individual droplet histories of solvent evaporation behavior and the dynamics of charge loss to progeny droplets during Rayleigh discharge events. On average, methanol droplets discharge at 127% their Rayleigh limit of charge, q(R), and release 25% of the net charge. Charge loss from methanol/2-methoxyethanol droplets behaves similarly to pure 2-methoxyethanol droplets which release approximately 28% of their net charge. Binary methanol droplets containing up to 50% tert-butanol discharge at a lower percent q(R) than pure methanol and release a greater fraction of their net charge. Mixed 99% methanol/1% m-nitrobenzyl alcohol droplets possess discharge characteristics similar to those of methanol. However, droplets of methanol containing 2% m-nitrobenzyl evaporate down to a fixed size and charge that remains constant with no observable discharges. Quasi-steady-state evaporation models accurately describe observed evaporation phenomena in which methanol/tert-butanol droplets evaporate at a rate similar to that of pure methanol and methanol/2-methoxyethanol droplets evaporate at a rate similar to that of 2-methoxyethanol. We compare these results to previous Rayleigh discharge experiments and discuss the implications for binary solvents in electrospray mass spectrometry (ESI-MS) and field-induced droplet ionization mass spectrometry (FIDI-MS). PMID:19848399

The VAST survey is a wide-field survey that observes with unprecedented instrument sensitivity (0.5 mJy or lower) and repeat cadence (a goal of 5 seconds) that will enable novel scientific discoveries related to known and unknown classes of radio transients and variables. Given the unprecedented observing characteristics of VAST, it is important to estimate source classification performance, and determine best practices prior to the launch of ASKAP's BETA in 2012. The goal of this study is to identify light curve characterization and classification algorithms that are best suited for archival VAST light curve classification. We perform our experiments on light curve simulations of eight source types and achieve best case performance of approximately 90% accuracy. We note that classification performance is most influenced by light curve characterization rather than classifier algorithm.

An original method based upon high-performance liquid chromatography coupled to electrospray ionization mass spectrometry has been developed for corticosterone (B) quantification in human serum. After extraction by diethyl ether using triamcinolone (T) as an internal standard, solutes are separated on a C18 microbore column (250 X 1.0 mm, I.D.), using acetonitrile-water-formic acid (40:59.9:0.1, v/v/v) as the mobile phase (flow-rate 40 microl/min). Detection is performed on an API 1 single quadrupole mass spectrometer equipped with a ESI interface and operated in positive ionization mode. Corticosterone quantifications were realized by computing peak area ratios (B/T) of the serum extracts analyzed in SIM mode (m/z 347 and m/z 395 for B and T. respectively), and comparing them with the calibration curve (r=0.998). PMID:10360442

Graphing polar curves typically involves a combination of three traditional techniques, all of which can be time-consuming and tedious. However, an alternative method--graphing the polar function on a rectangular plane--simplifies graphing, increases student understanding of the polar coordinate system, and reinforces graphing techniques learned…

A procedure that allows students to view an entire bacterial growth curve during a two- to three-hour student laboratory period is described. Observations of the lag phase, logarithmic phase, maximum stationary phase, and phase of decline are possible. A nonpathogenic, marine bacterium is used in the investigation. (KR)

Maintains that teachers and textbook graphics follow the same basic pattern in illustrating changes in demand curves when product prices increase. Asserts that the use of computer graphics will enable teachers to be more precise in their graphic presentation of price elasticity. (CFR)

We present a robust and computationally efficient numerical scheme for simulating steady electrohydrodynamic atomization processes (electrospray). The main simplification assumed in this scheme is that all the free electrical charges are distributed over the interface. A comparison of the results with those calculated with a volume-of-fluid method showed that the numerical scheme presented here accurately describes the flow pattern within the entire liquid domain. Experiments were performed to partially validate the numerical predictions. The simulations reproduced accurately the experimental shape of the liquid cone jet, providing correct values of the emitted electric current even for configurations very close to the cone-jet stability limit. PMID:23005852

Desorption electrospray ionization (DESI)-mass spectrometry facilitates the ambient chemical analysis of a variety of surfaces. Here we describe the protocol for using DESI imaging to measure the distributions of small prebiotically relevant molecules on granite surfaces. Granites that contain a variety of juxtaposed mineral species were reacted with formamide in order to study the role of local mineral environment on the production of purines and pyrimidines. The mass spectrometry imaging (MSI) methods described here can also be applied to the surface analysis of rock samples involved in other applications such as petroleum or environmental chemistries. PMID:25361668

Fluorescent nanodroplets of liquid crystal (LC) were generated by the electrospray deposition of LC solvent containing rhodamine 6G (Rh6G) dye molecules. The shape and density of the nanodroplets strongly depended on the concentration of LC diluted with ethanol solution. The fluorescent spectra from the Rh6G molecules in LC nanodroplets were obviously blue-shifted compared with the LC films of the bulk state. Furthermore, the LC nanodroplets were dispersed on a metallic nanograting formed by optically modifying an azobenzene thin-film layer under the metallic film. The nanodroplets were size-selectively aligned on the metallic nanograting.

Gradual corrosion of stainless steel electrospray emitters under conditions of normal use generates surface irregularities that can promote electrical discharge. The increased emission current affects the electrochemical reactions associated with the spray process. When sampling the peptide Aβ(1–40), this is manifest by oxidation of methionine at position 35 to methionine sulfoxide. The resultant mass shift and reduced sensitivity can adversely affect H/D exchange experiments. These effects can be avoided by adding a redox buffer or (preferably) by re-polishing the emitter, especially to a rounded geometry. PMID:17249640

A practical and rapid method based on electrospray ionization quadrupole-time of flight mass spectrometry (ESI-Q-ToF MS) was developed for detecting activities of both acetylcholinesterase IAChEI and glutathione S-transferase (GST). The simultaneous study of these two enzyme activities is significant for studying human bio-functions, especially for those who take in toxic compounds and have a risk of disease. Here, the enzyme activities were represented by the conversion of enzymatic substrates and determined by quantitatively analyzing enzymatic substrates. Different internal standards were used to quantify each enzymatic substrate and the good linearity of calibration curves demonstrated the feasibility of the internal standards. The Michaelis-Menten constants (Km) of both GST and AChE were measured by this method and were consistent with values previously reported. Furthermore, we applied this approach to detect GST and AChE activities of whole bloods from four deceased and healthy people. The variation in enzyme activity was in accord with information from gas chromatography mass spectrometry [GC/MS). The screening of AChE and GST provided reliable results and strong forensic evidence. This method offers an alternative choice for detecting enzyme activities and is anticipated to have wide applications in pharmaceutical research and prevention in toxic compounds. PMID:23654197

Analysis of triacylglycerols (TAGs), found as complex mixtures in living organisms, is typically accomplished using liquid chromatography, often coupled to mass spectrometry. TAGs, weak bases not protonated using electrospray ionization, are usually ionized by adduct formation with a cation, including those present in the solvent (e.g., Na+). There are relatively few reports on the binding of TAGs with cations or on the mechanisms by which cationized TAGs fragment. This work examines binding efficiencies, determined by mass spectrometry and computations, for the complexation of TAGs to a range of cations (Na+, Li+, K+, Ag+, NH4 +). While most cations bind to oxygen, Ag+ binding to unsaturation in the acid side chains is significant. The importance of dimer formation, [2TAG + M]+ was demonstrated using several different types of mass spectrometers. From breakdown curves, it became apparent that two or three acid side chains must be attached to glycerol for strong cationization. Possible mechanisms for fragmentation of lithiated TAGs were modeled by computations on tripropionylglycerol. Viable pathways were found for losses of neutral acids and lithium salts of acids from different positions on the glycerol moiety. Novel lactone structures were proposed for the loss of a neutral acid from one position of the glycerol moiety. These were studied further using triple-stage mass spectrometry (MS3). These lactones can account for all the major product ions in the MS3 spectra in both this work and the literature, which should allow for new insights into the challenging analytical methods needed for naturally occurring TAGs.

Improper treatment and disposal of perchlorate can be an environmental hazard in regions where solid rocket motors are used, tested, or stored. The solubility and mobility of perchlorate lends itself to ground water contamination, and some of these sources are used for drinking water. Perchlorate in drinking water has been determined at sub-mug l(-1) levels by extraction of the ion-pair formed between the perchlorate ion and a cationic surfactant with electrospray-mass spectrometry detection. Confidence in the selective quantification of the perchlorate ion is increased through both the use of the mass based detection as well as the selectivity of the ion pair. This study investigates several extraction solvents and experimental work-up procedures in order to achieve high sample throughput. The method detection limit for perchlorate based on 3.14sigma(n-1) of seven replicate injections was 300 ng l(-1) (parts-per-trillion) for methylene chloride extraction and 270 ng l(-1) for methyl isobutyl ketone extraction. Extraction with methylene chloride produces linear calibration curves, enabling standard addition to be used to quantify perchlorate in drinking water. Perchlorate determination of a contaminated water compared favorably with results determined by ion chromatography. PMID:18967987

Developmentalists are often interested in understanding change processes, and growth models are the most common analytic tool for examining such processes. Nonlinear growth curves are especially valuable to developmentalists because the defining characteristics of the growth process such as initial levels, rates of change during growth spurts, and…

In order to determine procedures for appropriate model selection of technological growth curves, numerous time series that were representative of growth behavior were collected and categorized according to data characteristics. Nine different growth curve models were each fitted onto the various data sets in an attempt to determine which growth curve models achieved the best forecasts for differing types of growth data. The analysis of the results gives rise to a new approach for selecting appropriate growth curve models for a given set of data, prior to fitting the models, based on the characteristics of the data sets. 58 refs., 9 tabs.

A rapid method for vapor pressure measurement was developed and used to derive the vapor pressure curve of the thermally labile peroxide-based explosive hexamethylene triperoxide diamine (HMTD) over the temperature range from 28 to 80 °C. This method uses a controlled flow of vapor from a solid-phase HMTD source that is presented to an ambient-pressure-ionization mass spectrometer equipped with a secondary-electrospray-ionization (SESI) source. The subpart-per-trillion sensitivity of this system enables direct detection of HMTD vapor through an intact [M + H](+) ion in real time at temperatures near 20 °C. By calibrating this method using vapor sources of cocaine and heroin, which have known pressure-temperature (P-T) curves, the temperature dependence of HMTD vapor was determined, and a Clausius-Clapeyron plot of ln[P (Pa)] vs 1/[T (K)] yielded a straight line with the expression ln[P (Pa)] = {(-11091 ± 356) × 1/[T (K)]} + 25 ± 1 (error limits are the standard error of the regression analysis). From this equation, the sublimation enthalpy of HMTD was estimated to be 92 ± 3 kJ/mol, which compares well with the theoretical estimate of 95 kJ/mol, and the vapor pressure at 20 °C was estimated to be ∼60 parts per trillion by volume, which is within a factor of 2 of previous theoretical estimates. Thus, this method provides not only the first direct experimental determination of HMTD vapor pressure but also a rapid, near-real-time capability to quantitatively measure low-vapor-pressure compounds, which will be useful for aiding in the development of training aids for bomb-sniffing canines. PMID:26505487

Recently a number of techniques have combined laser ablation with liquid capture for mass spectrometry spot sampling and imaging applications. The newly developed noncontact liquid-vortex capture probe has been used to efficiently collect material ablated by a 355 nm UV laser in a continuous flow solvent stream in which the captured material dissolves and then undergoes electrospray ionization. This sampling and ionization approach has produced what appears to be classic electrospray ionization spectra; however, the `softness' of this sampling/ionization process versus simple electrospray ionization has not been definitely determined. In this work, a series of benzylpyridinium salts were employed as thermometer ions to compare internal energy distributions between electrospray ionization and the UV laser ablation/liquid-vortex capture probe electrospray combination. Measured internal energy distributions were identical between the two techniques, even with differences in laser fluence (0.7-3.1 J cm-2) and when using UV-absorbing or non-UV-absorbing sample substrates. These data, along with results from the analysis the biological molecules bradykinin and angiotensin III indicated that the ions or their fragments formed directly by UV laser ablation that survive the liquid capture/electrospray ionization process were likely to be an extremely small component of the total ion signal observed. Instead, the preponderate neutral molecules, clusters, and particulates ejected from the surface during laser ablation, subsequently captured and dissolved in the flowing solvent stream, then electrosprayed, were the principal source of the ion signal observed. Thus, the electrospray ionization process used controls the overall `softness' of this technique.

Due to their low polarities and dielectric constants, analytes in solvents such as hexane, chloroform, and ethyl acetate exhibit poor electrospray ionization (ESI) efficiency. These are deemed to be "non-ESI-friendly" solvents. Continuous flow extractive desorption electrospray ionization (CF-EDESI) is a novel ambient ionization technique that was recently developed in our group to manipulate protein charge distributions. Here we demonstrate its potential for ionizing analytes from non-ESI-friendly solvents. This feature makes CF-EDESI attractive to the general analytical community due to its apparent potential in lipidomics, normal phase separations, and hyphenation of mass spectrometry with HPLC-NMR systems. In this context, interest was subsequently initiated to discern mechanistic aspects of CF-EDESI. To achieve this, mechanistic experiments associated with a seemingly similar ambient ionization technique, extractive electrospray ionization (EESI), were emulated to compare CF-EDESI and EESI. Analysis of a series of fatty acids in multiple solvents in the negative ionization mode revealed differences between the two techniques. Whereas EESI has been previously shown to operate via extraction of analytes into the spray solvent, data presented here for CF-EDESI point toward a liquid-liquid mixing process to facilitate ionization. Further, a partial factorial design experiment was performed to evaluate the effects of different experimental variables on signal intensity. Sample flow rate was confirmed to be among the most significant factors to affect sensitivity. As a whole, the work presented provides greater insight into a new ambient ionization process, which exhibits expanded capabilities over conventional ESI; in this case, for direct analysis from non-ESI-friendly solvents. PMID:23498125

The elliptic curve method (ECM) is one of the best factorization methods available. It is possible to use hyperelliptic curves instead of elliptic curves but it is in theory slower. We use special hyperelliptic curves and Kummer surfaces to reduce the complexity of the algorithm. Our implementation GMP-HECM is faster than GMP-ECM for factoring large numbers.

We give an explanation for the polarity, localization, shape, size, and initiation of subduction zones on Earth. By considering a soft, thin, curved lithospheric cap with either elastic or viscous rheology supported by a thick, nearly incompressible mantle, we find two different characteristic subduction geometries arise depending on boundary conditions: (1) plate boundaries where subduction results primarily from the gravitational body force (free subduction) have characteristic plate lengths and form arc-shaped dimpled segments resulting from the competition between bending and stretching in edge buckling modes of thin spherical shells, and (2) subduction zones due to localized applied loads that push one slab of thin, positively buoyant lithosphere beneath an overriding plate (forced subduction) form localized straight segments, consistent with the deformation of indented spherical shells. Both types of subduction are nonlinear subcritical instabilities, so small perturbations in the mechanical properties of the lithosphere have pronounced effects on subduction initiation and evolution. Yet in both cases, geometric relationships determined by the shape of the Earth itself play the most critical role in controlling the basic morphology and characteristic length scales of subduction zones.

In most animal species, vision is mediated by compound eyes, which offer lower resolution than vertebrate single-lens eyes, but significantly larger fields of view with negligible distortion and spherical aberration, as well as high temporal resolution in a tiny package. Compound eyes are ideally suited for fast panoramic motion perception. Engineering a miniature artificial compound eye is challenging because it requires accurate alignment of photoreceptive and optical components on a curved surface. Here, we describe a unique design method for biomimetic compound eyes featuring a panoramic, undistorted field of view in a very thin package. The design consists of three planar layers of separately produced arrays, namely, a microlens array, a neuromorphic photodetector array, and a flexible printed circuit board that are stacked, cut, and curved to produce a mechanically flexible imager. Following this method, we have prototyped and characterized an artificial compound eye bearing a hemispherical field of view with embedded and programmable low-power signal processing, high temporal resolution, and local adaptation to illumination. The prototyped artificial compound eye possesses several characteristics similar to the eye of the fruit fly Drosophila and other arthropod species. This design method opens up additional vistas for a broad range of applications in which wide field motion detection is at a premium, such as collision-free navigation of terrestrial and aerospace vehicles, and for the experimental testing of insect vision theories. PMID:23690574

In most animal species, vision is mediated by compound eyes, which offer lower resolution than vertebrate single-lens eyes, but significantly larger fields of view with negligible distortion and spherical aberration, as well as high temporal resolution in a tiny package. Compound eyes are ideally suited for fast panoramic motion perception. Engineering a miniature artificial compound eye is challenging because it requires accurate alignment of photoreceptive and optical components on a curved surface. Here, we describe a unique design method for biomimetic compound eyes featuring a panoramic, undistorted field of view in a very thin package. The design consists of three planar layers of separately produced arrays, namely, a microlens array, a neuromorphic photodetector array, and a flexible printed circuit board that are stacked, cut, and curved to produce a mechanically flexible imager. Following this method, we have prototyped and characterized an artificial compound eye bearing a hemispherical field of view with embedded and programmable low-power signal processing, high temporal resolution, and local adaptation to illumination. The prototyped artificial compound eye possesses several characteristics similar to the eye of the fruit fly Drosophila and other arthropod species. This design method opens up additional vistas for a broad range of applications in which wide field motion detection is at a premium, such as collision-free navigation of terrestrial and aerospace vehicles, and for the experimental testing of insect vision theories. PMID:23690574

Proteins are important substances in living organisms and characterization of proteins is an indispensible part for protein study. Analysis of proteins using electrospray ionization-mass spectrometry (ESI-MS) with porous substrates was investigated in this study. The results revealed that the ionization process had two stages. At the first stage, mobility and resulting spectra of proteins were similar to those obtained with conventional capillary-based ESI-MS. At the second stage, hydrophobic-hydrophobic interactions between proteins and the tip surfaces played an important role in mobility and detectability of protein ions, which were size and shape dependent, and a linear relationship could be found between the peak area of selected ion chromatogram and the cross section of protein ions. Preparative separation of proteins could be achieved by collecting the proteins remained on the porous substrates. These results led us to propose that electrospray ionization from porous substrates offer a potential approach for analysis of proteins and investigation of protein structures and conformations. PMID:27149434

We report here the development of a corona discharge (CD) initiated electrochemical (EC) electrospray ionization (ESI) technique using a standard electrospray ion source. This is a new ionization technique distinct from ESI, electrochemistry inherent to ESI, APCI, and techniques using hydroxyl radicals produced under atmospheric pressure conditions. By maximizing the observable CD at the tip of a stainless steel ESI capillary, efficient electrochemical oxidation of electrochemically active compounds is observed. For electrochemical oxidation to be observed, the ionization potential of the analyte must be lower than Fe. Ferrocene labeled compounds were chosen as the electrochemically active moiety. The electrochemical cell in the ESI source was robust and generated ions with selectivity according to the ionization potential of the analytes and up to zeptomolar sensitivity. Our results indicate that CD initiated electrochemical ionization has the potential to become a powerful technique to increase the dynamic range, sensitivity and selectivity of ESI experiments. Synopsis Using a standard ESI source a corona discharge initiated electrochemical ionization technique was established resulting from the electrochemistry occurring at the CD electrode surface. PMID:19747843

A magnetic-bottle time-of-flight (TOF) photoelectron spectrometer, coupled with an electrospray ionization source, has been developed for the investigation of multiply charged anions in the gas phase. Anions formed in the electrospray source are guided by a radio-frequency quadrupole ion guide into a quadrupole ion trap, where the ions are accumulated. A unique feature of this apparatus involves the coupling of a TOF mass spectrometer to the ion trap with perpendicular ion extraction. The ion trap significantly improves the duty cycle of the experiments and allows photodetachment experiments to be performed with low repetition-rate lasers (10{endash}20 Hz). This novel combination makes the photodetachment photoelectron spectroscopy studies of multiply charged anions possible for the first time. Furthermore, the perpendicular extraction of ions, pulsed out of the ion trap, to the TOF mass spectrometer allows the ion energies to be conveniently referenced to ground, simplifying the configuration of the TOF mass spectrometer and the subsequent magnetic-bottle TOF photoelectron spectrometer. The mass resolution (M/{Delta}M) achieved is about 800 for smaller ions. The magnetic-bottle photoelectron spectrometer resolution is about 11 meV full width at half maximum for 0.5 eV photoelectrons with an overall resolution of {Delta}E/E{approximately}2{percent}. The detailed design, construction, and operation of the new apparatus are presented. {copyright} {ital 1999 American Institute of Physics.}

During the analysis of surface spotted analytes using desorption electrospray ionization mass spectrometry (DESI-MS), abundant ions are sometimes observed that appear to be the result of oxygen addition reactions. In this investigation, the effect of sample aging, the ambient lab environment, spray voltage, analyte surface concentration, and surface type on this oxidative modification of spotted analytes, exemplified by tamoxifen and reserpine, during analysis by desorption electrospray ionization mass spectrometry was studied. Simple exposure of the samples to air and to ambient lighting increased the extent of oxidation. Increased spray voltage lead also to increased analyte oxidation, possibly as a result of oxidative species formed electrochemically at the emitter electrode or in the gas - phase by discharge processes. These oxidative species are carried by the spray and impinge on and react with the sampled analyte during desorption/ionization. The relative abundance of oxidized species was more significant for analysis of deposited analyte having a relatively low surface concentration. Increasing spray solvent flow rate and addition of hydroquinone as a redox buffer to the spray solvent were found to decrease, but not entirely eliminate, analyte oxidation during analysis. The major parameters that both minimize and maximize analyte oxidation were identified and DESI-MS operational recommendations to avoid these unwanted reactions are suggested.

This Atlas was developed to serve engineers who are looking for fatigue data on a particular metal or alloy. Having these curves compiled in a single book will also facilitate the computerization of the involved data. It is pointed out that plans are under way to make the data in this book available in ASCII files for analysis by computer programs. S-N curves which typify effects of major variables are considered along with low-carbon steels, medium-carbon steels, alloy steels, HSLA steels, high-strength alloy steels, heat-resisting steels, stainless steels, maraging steels, cast irons, and heat-resisting alloys. Attention is also given to aluminum alloys, copper alloys, magnesium alloys, molybdenum, tin alloys, titanium and titanium alloys, zirconium, steel castings, closed-die forgings, powder metallurgy parts, composites, effects of surface treatments, and test results for component parts.

A biometric system suitable for validating user identity using only mouse movements and no specialized equipment is presented. Mouse curves (mouse movements with little or no pause between them) are individually classied and used to develop classication histograms, which are representative of an individual's typical mouse use. These classication histograms can then be compared to validate identity. This classication approach is suitable for providing continuous identity validation during an entire user session.

Scoliosis, an abnormal side-to-side curve of the spine with associated vertebral rotation, affects as many as 4% of all adolescents. Several different categories of scoliosis exist, and treatment can range from observation and follow-up to bracing and surgical correction. This article discusses special imaging series for scoliosis and emphasizes the need for proper radiation protection techniques for patients with scoliosis, most of whom are girls in their early to mid-teens. PMID:17848532

Desorption electrospray ionization mass spectrometry was investigated as a means to qualitatively identify and to quantify analytes directly from developed normal-phase thin-layer chromatography plates. The atmospheric sampling capillary of a commercial ion trap mass spectrometer was extended to permit sampling and ionization of analytes in bands separated on intact TLC plates (up to 10 cmx10 cm). A surface positioning software package and the appropriate hardware enabled computer-controlled surface scanning along the length of development lanes or at fixed Rf value across the plates versus the stationary desorption electrospray emitter. Goldenseal (Hydrastis canadensis) and related alkaloids and commercial dietary supplements were used as standards and samples. Alkaloid standards and samples were spotted and separated on aluminum- or glass-backed plates using established literature methods. The mass spectral signal levels as a function of desorption spray solvent were investigated with acetonitrile proving superior to methanol. The detection levels (approximately 5 ng each or 14-28 pmol) in mass spectral full-scan mode were determined statistically from the calibration curves (2.5-100 pmol) for the standards berberine, palmatine, and hydrastinine spotted as a mixture and separated on the plates. Qualitative screening of the major alkaloids present in six different over-the-counter "goldenseal" dietary supplements was accomplished by obtaining full-scan mass spectra during surface scans along the development lane in the direction of increasing Rf value. In one sample, alkaloids were detected that strongly suggested the presence of at least one additional herb undeclared on the product label. These same data indicated the misidentification of one of the alkaloids in the TLC literature. Quantities of the alkaloids present in two of the samples determined using the mass spectral data were in reasonable agreement with the label values, indicating the quantitative

The Stephan Curve has played a dominant role in caries research over the past several decades. What is so remarkable about the Stephan Curve is the plethora of interactions it illustrates and yet acid production remains the dominant focus. Using sophisticated technology, it is possible to measure pH changes in plaque; however, these observations may carry a false sense of accuracy. Recent observations have shown that there may be multiple pH values within the plaque matrix, thus emphasizing the importance of the milieu within which acid is formed. Although acid production is indeed the immediate proximate cause of tooth dissolution, the influence of alkali production within plaque has received relative scant attention. Excessive reliance on Stephan Curve leads to describing foods as "safe" if they do not lower the pH below the so-called "critical pH" at which point it is postulated enamel dissolves. Acid production is just one of many biological processes that occur within plaque when exposed to sugar. Exploration of methods to enhance alkali production could produce rich research dividends. PMID:23224410

Hexanitrohexaazaisowurtzitane, (C6H6N12O12, MW 438) {CL-20}, is a high-energy propellent that has been recently developed and successfully tested (Nielsen et al. 1998). CL-20 releases more energy on ignition and is more stable to accidental detonation than currently used energetic materials. It is expected to replace many of the energetic materials currently being used by the Department of Defense (DoD). The EPA method 8330 (EPA 1997) for the analysis of explosives and metabolites in soils calls for the use of UV/Vis detection. High performance liquid chromatography has been used to quantify CL-20 and precursor concentration (Bazaki et al. 1998`) at relatively high concentrations. Fourier transform infrared (FTIR) spectroscopy has been used to identify different crystal forms of CL-20 (4 isomers; Kim et al. 1998). Campbell et al. (1997) utilized particle beam mass spectrometry for the analysis of enzymatic degradation of explosives. Introduction and recent improvements of ionization techniques such as electrospray (ES) have allowed the mass spectrometer to become more widely used in liquid chromatography. Schilling(1996) also examined explosive components and metabolites using electrospray (ES) and atmospheric pressure chemical ionization (APCI) liquid chromatography/mass spectrometry (LC/MS). Schilling’s results showed that compared to thermospray LC/MS, APCI and ES were more sensitive than thermospray by at least an order of magnitude. 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), 10 nitroso-RDX metabolites, and other munitions in ground water have been analyzed using solid phase extraction and isotope dilution liquid chromatography-APCI mass spectrometry (Cassada et al. 1999). The method detection limits indicate that nitramine and nitroaromatic compounds can be routinely determined in ground water samples using electrospray LC/MS with concentration techniques utilizing solid-phase extraction. Miller et al. (1996) studied nitrated explosives with mobile phase

The performance of a diagnostic test is summarized by its receiver operating characteristic (ROC) curve. Under quite natural assumptions about the latent variable underlying the test, the ROC curve is convex. Empirical data on a test's performance often comes in the form of observed true positive and false positive relative frequencies under varying conditions. This paper describes a family of regression models for analyzing such data. The underlying ROC curves are specified by a quality parameter delta and a shape parameter mu and are guaranteed to be convex provided delta > 1. Both the position along the ROC curve and the quality parameter delta are modeled linearly with covariates at the level of the individual. The shape parameter mu enters the model through the link functions log(p mu) - log(1 - p mu) of a binomial regression and is estimated either by search or from an appropriate constructed variate. One simple application is to the meta-analysis of independent studies of the same diagnostic test, illustrated on some data of Moses, Shapiro, and Littenberg (1993). A second application, to so-called vigilance data, is given, where ROC curves differ across subjects and modeling of the position along the ROC curve is of primary interest. PMID:10985227

The notion that human learning follows a smooth power law (PL) of diminishing gains is well-established in psychology. This characteristic is observed when multiple curves are averaged, potentially masking more complex dynamics underpinning the curves of individual learners. Here, we analyzed 25,280 individual learning curves, each comprising 500 measurements of cognitive performance taken from four cognitive tasks. A piecewise PL (PPL) model explained the individual learning curves significantly better than a single PL, controlling for model complexity. The PPL model allows for multiple PLs connected at different points in the learning process. We also explored the transition dynamics between PL curve component pieces. Performance in later pieces typically surpassed that in earlier pieces, after a brief drop in performance at the transition point. The transition rate was negatively associated with age, even after controlling for overall performance. Our results suggest at least two processes at work in individual learning curves: locally, a gradual, smooth improvement, with diminishing gains within a specific strategy, which is modeled well as a PL; and globally, a discrete sequence of strategy shifts, in which each strategy is better in the long term than the ones preceding it. The piecewise extension of the classic PL of practice has implications for both individual skill acquisition and theories of learning. PMID:25711183

In this paper, we investigate the Smarandache curves according to Sabban frame of fixed pole curve which drawn by the unit Darboux vector of the Bertrand partner curve. Some results have been obtained. These results were expressed as the depends Bertrand curve.

A device for analyzing commutating characteristics of a motor or generator includes a holder for supporting a plurality of probes adjacent a brush of the motor or generator. Measurements of electrical current characteristics of the probes provides information useful in analyzing operation of the machine. Methods for employing a device in accordance with the invention are also disclosed.

The analysis of Stevia leaves has been demonstrated without any sample preparation using desorption electrospray ionization (DESI) mass spectrometry. Direct rapid analysis was achieved using minimal amounts of sample ( approximately 0.15 cm x 0.15 cm leaf fragment). Characteristic constituents of the Stevia plant are observed in both the positive and negative ion modes including a series of diterpene 'sweet' glycosides. The presence of the glycosides was confirmed via tandem mass spectrometry analysis using collision-induced dissociation and further supported by exact mass measurements using an LTQ-Orbitrap. The analysis of both untreated and hexane-extracted dry leaves proved that DESI can be successfully used to analyze untreated leaf fragments as identical profiles were obtained from both types of samples. Characterization and semi-quantitative determination of the glycosides was achieved based on the glycoside profile within the full mass spectrum. In addition, the presence of characteristic glycosides in an all-natural commercial Stevia dietary supplement was confirmed. This study provides an example of the application of DESI to direct screening of plant materials, in this case diterpene glycosides. PMID:19381377

We report on the development of a single-propellant ElectroSpray (ES) microthruster able to: (a) cover a wide range of specific impulse (Isp) and thrust at high propulsion efficiency, and (b) provide macroscopic thrust via micro-fabricated emitter arrays. The electrospray is a mature technology for the emission of fast nanodroplets at a propulsive efficiency larger than 50% over the full Isp range. The size of the droplets depends on the propellant flow rate and the physical properties of the electrolyte, especially the electric conductivity. To achieve a useful thrust one needs to multiplex the ES by operating many in parallel, which we achieve via silicon microfabrication of arrays of multiple and identical nozzles. The Multiplexed Electrospray (MES) micro-thruster is composed mainly of two electrodes: a nozzle-array and an extractor electrode, between which the electric field needed to form the ES is established. We tested nozzle arrays with up to 37 capillaries, that are spaced 1mm apart, with ID/OD = 10/30μ m. The capillaries are filled with 2.01μ m silicon dioxide beads to increase the hydraulic impedance and ensure uniform flow rate through the different emitters. A third electrode (accelerator) is mounted downstream the extractor to accelerate the droplets, thereby increasing the microthruster performance. The system is packaged in an alumina casing for electrical insulation and propellant feed. Tests run in a vacuum chamber at a pressure ≤ 10-5 mbar demonstrated reliable operation for several hours with a relatively high beam energy of 7.56kV. The 37-nozzle MES device was tested with the ionic liquid ethylammonium nitrate (EAN), at estimated total flow rates between 1.2 and 14 μ L/h, emitted currents between 14.2 and 23.0 μ A, specific impulse ranging between 710 and 1930s, and thrust ranging between 7.5 and 33 μ N. EAN is well suited to cover a relatively broad range of charge/mass- at an average propulsion efficiency of 66%. With further scale

We report for the first time a novel erythrocyte-like graphene microsphere (ELGMs) which can be produced with high quality and mass production capability via electrospray assisted self-assembly. Through simple electrospray treatment of GO suspension into coagulation bath followed by chemical reduction, large quantity of ELGMs with uniform morphology and size can be obtained with production rate of around 2.4 mg/h. Compared with other 3D structures, the ELGMs have a very interesting structural characteristic of perfect exterior doughnut shape and interior porous network. Accordingly, the as-prepared porous ELGMs exhibit excellent capability for fast and recyclable removal of oil and toxic organic solvents from water, reaching up to 216 times of its weight in absorption efficiency, which is tens of times higher than that of conventional sorbent materials. It is strongly believed that the novel hierarchical graphene structures and synergy among different techniques will lead to more future advances in graphene applications. PMID:24270315

Nearly a decade after first commercialization, high field asymmetric waveform ion mobility spectrometry (FAIMS) has yet to find its place in routine chemical analysis. Prototypes have been used to demonstrate the utility of this separation technique combined with mass spectrometry (MS). Unfortunately, first generation commercial FAIMS instruments have gone practically unused by early adopters. Here, we show this to be due to poor ion transmission in the FAIMS-MS source interface. We present simple instrumental modifications and optimization of experimental conditions to achieve good performance from the first generation commercial FAIMS device (the Ionalytics Selectra) coupled to a high resolution Q-TOF-MS. In combination with nanospray ionization, we demonstrate for the first time the nontarget analysis of urine by FAIMS with minimal sample preparation. We show the unique suitability of electrospray ionization (ESI)-FAIMS-MS for identification of low abundance species such as urinary biomarkers of damage of nucleic acids in a complex biological matrix. The elimination of electrospray noise and matrix components by FAIMS and the continuous flow of analytes through FAIMS for accurate and tandem mass analysis produce high quality spectral data suitable for structural identification of unknowns. These characteristics make ESI-FAIMS-MS ideal for nontarget identification, even when compared to high efficiency LC-ESI-MS. PMID:21978137

We report for the first time a novel erythrocyte-like graphene microsphere (ELGMs) which can be produced with high quality and mass production capability via electrospray assisted self-assembly. Through simple electrospray treatment of GO suspension into coagulation bath followed by chemical reduction, large quantity of ELGMs with uniform morphology and size can be obtained with production rate of around 2.4 mg/h. Compared with other 3D structures, the ELGMs have a very interesting structural characteristic of perfect exterior doughnut shape and interior porous network. Accordingly, the as-prepared porous ELGMs exhibit excellent capability for fast and recyclable removal of oil and toxic organic solvents from water, reaching up to 216 times of its weight in absorption efficiency, which is tens of times higher than that of conventional sorbent materials. It is strongly believed that the novel hierarchical graphene structures and synergy among different techniques will lead to more future advances in graphene applications. PMID:24270315

An electrospray ion source includes a chamber including a channel region therein, the channel including at least one inlet for directing a solution into the channel and at least a first and a second outlet for transmitting the solution or derivatives therefrom out from channel. Structure for separating ions in the solution is provided from separating the solution into at least a first and a second flow stream portion. The first flow stream portion is enriched in negative ions and the second flow stream portion is enriched in positive ions. The first flow stream portion is adapted to exit the chamber through the first outlet while the second flow stream portion is adapted to exit the chamber through the second outlet. A method of charge separation can include the step of simultaneously providing at least two gas phase ion stream portions having opposite polarity.

A precise understanding of electrosprays is highly interesting as the complexity of micro-technology (such as nano-material processing, spacecraft propulsion and mass-spectrometers) systems increases. A multi-component CFD-based model coupling fluid dynamics, charged species dynamics and electric field is developed. The simulations describe the charged fluid interface with emphasis on the Taylor cone formation and cone-jet transition under the effect of a electric field. The goal is to recapture this transition from a rounded liquid interface into a Taylor cone from an initial uniform distribution, without making assumptions on the behaviour, geometry or charge distribution of the system. The time evolution of the interface highlights the close interaction among space charge, coulombic forces and the surface tension, which appear as governing and competing processes in the transition. The results from the coupled formalism provide valuable insights on the physical phenomena and will be applied to a colloid thruster for small spacecrafts.

A system and method for analyzing molecular constituents of a composition sample includes: forming a solution of the sample, separating the solution by capillary zone electrophoresis into an eluent of constituents longitudinally separated according to their relative electrophoretic mobilities, electrospraying the eluent to form a charged spray in which the molecular constituents have a temporal distribution; and detecting or collecting the separated constituents in accordance with the temporal distribution in the spray. A first high-voltage (e.g., 5-100 KVDC) is applied to the solution. The spray is charged by applying a second high voltage (e.g., .+-.2-8 KVDC) between the eluent at the capillary exit and a cathode spaced in front of the exit. A complete electrical circuit is formed by a conductor which directly contacts the eluent at the capillary exit.

We have developed a mass spectrometry-based method that allows one to accurately determine the glucose concentration of tear fluid. We used a 1 microL micro-capillary to collect tear fluid from the tear meniscus with minimal irritation of the eye. We analyzed the 1 muL volume of collected tear fluid with liquid-chromatography electrospray ionization mass spectrometry with the use of D-glucose-6,6-d2 as an internal standard. Repeated measurements and a recovery experiment on pooled, onion-induced tears showed that the analysis of the glucose in tears was precise (4% relative standard deviation) and provided 100% recovery. We found the tear glucose concentration of one fasting nondiabetic subject to be 13 to 51 microM while the onion-induced tear glucose concentration of a different nondiabetic subject to be 211 to 256 microM. PMID:17084090

We have developed a mass spectrometry-based method which allows one to accurately determine the glucose concentration of tear fluid. We used a 1 μL micro-capillary to collect tear fluid from the tear meniscus with minimal irritation of the eye. We analyzed the 1 μL volume of collected tear fluid with liquid-chromatography electrospray ionization mass spectrometry with the use of D-glucose-6,6-d2 as an internal standard. Repeated measurements and a recovery experiment on pooled, onion-induced tears showed that the analysis of the glucose in tears was precise (4% relative standard deviation) and provided 100% recovery. We found the tear glucose concentration of one fasting non-diabetic subject to be 13 to 51 μM while the onion-induced tear glucose concentration of a different non-diabetic subject to be 211 to 256 μM. PMID:17084090

This study shows that electrospray ionization mass spectrometry (ESI-MS), combined with a heated turbo ion-spray interface, allows monitoring protein stabilization by glycerol in solution. Measurements obtained with the two proteins lysozyme and cytochrome c are presented. The observed mass-to-charge (m/z) distributions reveal the stabilizing effect of the additive on the protein conformations against temperature and acid-induced unfolding, as well as against denaturation by acetonitrile. The data obtained with lysozyme allow detection of minor conformational changes upon glycerol addition to the native protein, and suggest that the protein structure in the presence of the additive is slightly compressed compared with its state in water. This result corroborates previous evidence obtained by nuclear magnetic resonance. It is also shown that analysis of the m/z distributions obtained by ESI-MS can lead to detection of partially folded and partially populated states in protein samples. PMID:11523091

A method to semiquantify urinary oligosaccharides from patients suffering from oligosaccharidurias is presented. 1-Phenyl-3-methyl-5-pyrazolone has been used to derivatize urinary oligosaccharides prior to analysis by electrospray ionization-tandem mass spectrometry (ESI-MS/MS). Disease-specific oligosaccharides were identified for several oligosaccharidurias, including GM1 gangliosidosis, GM2 gangliosidosis, sialic acid storage disease, sialidase/neuraminidase deficiency, galactosialidosis, I-cell disease, fucosidosis, Pompe and Gaucher diseases, and alpha-mannosidosis. The oligosaccharides were referenced against the internal standard, methyl lactose, to produce ratios for comparison with control samples. Elevations in specific urinary oligosaccharides were indicative of lysosomal disease and the defective catabolic enzyme. This method has been adapted to enable assay of large sample numbers and could readily be extended to other oligosaccharidurias and to monitor oligosaccharide levels in patients receiving treatment. It also has immediate potential for incorporation into a newborn screening program. PMID:16111643

A system and method for analyzing molecular constituents of a composition sample includes: forming a solution of the sample, separating the solution by capillary zone electrophoresis into an eluent of constituents longitudinally separated according to their relative electrophoretic mobilities, electrospraying the eluent to form a charged spray in which the molecular constituents have a temporal distribution; and detecting or collecting the separated constituents in accordance with the temporal distribution in the spray. A first high-voltage (e.g., 5--100 kVDC) is applied to the solution. The spray is charged by applying a second high voltage (e.g., [+-]2--8 kVDC) between the eluent at the capillary exit and a cathode spaced in front of the exit. A complete electrical circuit is formed by a conductor which directly contacts the eluent at the capillary exit. 10 figs.

Imaging resolution of desorption electrospray ionization mass spectrometry (DESI-MS) was investigated using printed patterns on paper and thin-layer chromatography (TLC) plate surfaces. Resolution approaching 40 m was achieved with a typical DESI-MS setup, which is approximately 5 times better than the best resolution reported previously. This improvement was accomplished with careful control of operational parameters (particularly spray tip-to-surface distance, solvent flow rate, and spacing of lane scans). Also, an appropriately strong analyte/surface interaction and uniform surface texture on the size scale no larger that the desired imaging resolution were required to achieve this resolution. Overall, conditions providing the smallest possible effective desorption/ionization area in the DESI impact plume region and minimizing the analyte redistribution on the surface during analysis led to the improved DESI-MS imaging resolution.

Composite coatings composed of carbonated calcium deficient hydroxyapatite (CDHA) and polylactic acid (PLA) were deposited on a PLA substrate surface via electrospraying. The operation parameters, structural properties, bioactivity, cell adhesion, and growth capability of as-fabricated PLA/CDHA coatings were investigated. The composite coating showed good biocompatibility and bioactivity. The deposited coating was also applied as a carrier to assist alendronate sodium (AS) local release. AS, an approved bisphosphonate drug used for the treatment of osteoporosis, was incorporated into a composite coating matrix via coelectrospraying. Its release behavior showed a long-term sustained release. This approach can be a potential coating technique for the surface modification of biopolymer implants. PMID:23594068

The claimed invention describes methods and apparatuses for manufacturing nano-aerosols and nano-structured materials based on the neutralization of charged electrosprayed products with oppositely charged electrosprayed products. Electrosprayed products include molecular ions, nano-clusters and nano-fibers. Nano-aerosols can be generated when neutralization occurs in the gas phase. Neutralization of electrospan nano-fibers with molecular ions and charged nano-clusters may result in the formation of fibrous aerosols or free nano-mats. Nano-mats can also be produced on a suitable substrate, forming efficient nano-filters.

Electrospray (ESI) ionization efficiencies (IE) of a set of 10 compounds differing by chemical nature, extent of ionization in solution (basicity), and by hydrophobicity (tetrapropylammonium and tetraethylammonium ion, triethylamine, 1-naphthylamine, N,N-dimethylaniline, diphenylphthalate, dimethylphtahalate, piperidine, pyrrolidine, pyridine) have been measured in seven mobile phases (three acetonitrile percentages 20%, 50%, and 80%, and three different pH-adjusting additives, 0.1% formic acid, 1 mM ammonia, pH 5.0 buffer combination) using the relative measurement method. MS parameters were optimized separately for each ion. The resulting relative IE data were converted into comparable logIE values by anchoring them to the logIE of tetrapropylammonium ion taking into account the differences of ionization in different solvents and thereby making the logIE values of the compounds comparable across solvents. The following conclusions were made from analysis of the data. The compounds with pK a values in the range of the solution pH values displayed higher IE at lower pH. The sensitivity of IE towards pH depends on hydrophobicity being very strong with pyridine, weaker with N,N-dimethylaniline, and weakest with 1-naphthylamine. IEs of tetraalkylammonium ions and triethylamine were expectedly insensitive towards solution pH. Surprisingly high IEs of phthalate esters were observed. The differences in solutions with different acetonitrile content and similar pH were smaller compared with the pH effects. These results highlight the importance of hydrophobicity in electrospray and demonstrate that high hydrophobicity can sometimes successfully compensate for low basicity.

Version 00 TRAX computes the resolution matrix and characteristic line widths and intensities for three-axis slow-neutron spectrometers with flat or curved, mosaic or perfect crystals, with or without Soller collimators or limiting diaphragms.

Discusses ways in which datalogging equipment can enable titration curves to be measured accurately and how computing power can be used to predict the shape of curves. Highlights include sources of error, use of spreadsheets to generate titration curves, titration of a weak acid with a strong alkali, dibasic acids, weak acid and weak base, and…

The catalog of Savage et al. (\\cite{ref27}) reporting colour excesses of 1415 stars from ANS photometry offers the opportunity to deeply investigate the characteristics of UV extinction curves which differ from the standard extinction of the diffuse interstellar medium. To this aim we have selected a sample of 252 curves, which have been compared with the relations derived by Cardelli et al. (\\cite{ref4}; CCM in the following) for a variety of R_V values in the range 2.4-5 and have been classified as normal if they fit at least one of the CCM curves or anomalous otherwise. We find that normal curves with small R_V are just as numerous as those with large R_V. The anomalous objects are arranged into two groups according to the strength of the bump at 0.217 mu . For a given value of c_2 this increases along the sequence: type A anomalous, normals and type B anomalous, suggesting that this sequence should correspond to an increase of the amount of small grains along the sightline. Considerations concerning the environmental characteristics indicate that the anomalous behaviour is not necessarily tied to the existence of dense gas clouds along the line of sight.

The detection and quantitation of four ethanolamines, tris(2-hydroxyethyl)amine (triethanolamine, TEA), N,N-bis(2-hydroxyethyl)methylamine (methyldiethanolamine, MDEA), N-(2-aminoethyl)ethanolamine (AEA), and N,N-diethylethanolamine (DEA), were achieved in wastewaters from two aerobic activated sludge bioreactors located in an industrial wastewater treatment plant. The streams had salt concentrations of approximately 3% and 7% by weight in Reactor 1 and Reactor 2, respectively. The use of liquid chromatography-electrospray ionization-tandem mass spectrometry avoided the need for some sample preparation steps such as extraction, concentration, and derivatization. Ion suppression in the electrospray, attributable to the presence of sodium clusters, was attenuated by a 10-fold dilution of the wastewaters with acetonitrile. A matrix-matched calibration model averted other potential interferences. For the compounds analyzed in selected reaction monitoring mode (TEA, MDEA, and DEA), the calibration curves presented linearity in a range of 10-1000microg/L with corresponding detection limits ranging from 2 to 11microg/L, depending upon the specific analyte and aqueous matrix. AEA was calibrated in selected ion monitoring mode (100-1000microg/L), with corresponding detection limits in the two wastewaters of 74.6 and 85.3microg/L, respectively. Overall good precision (<10%) and accuracy (97-110%) were achieved for both matrices, which fell within-laboratory reproducibility. Finally, the amines were introduced into six mixed liquor samples from both reactors and quantified following the reported protocol. Again, recoveries were close to 100% with a relative standard deviation of less than 10% in all cases. PMID:20006060

Results are presented of a wind-tunnel investigation made to determine the influence of the fuselage and tail surfaces on the rotary derivatives in yawing flight of a transonic-airplane configuration having 45 degrees sweptback wing and tail surfaces. The tests were run in the curved-flow test section of the Langley stability tunnel at a Reynolds number of 1.07 X 10 to the sixth power and consisted of balance measurements throughout the angle-of-attack range for several flight-path radii of curvature. The results are compared with data from forced-oscillation and free-oscillation tests, and a description of testing techniques used is included.

When physicians inspect an image, they make up a certain degree of confidence that the image are abnormal; p(t), or normal; n(t)[n(t)=1-p(t)]. After infinite time of the inspection, they reach the equilibrium levels of the confidence of p*=p(∞) and n*=n(∞). There are psychological conflicts between the decisions of normal and abnormal. We assume that the decision of "normal" is distracted by the decision of "abnormal" by a factor of k(1 + ap), and in an inverse direction by a factor of k(1 + bn), where k ( > 0) is a parameter that relates with image quality and skill of the physicians, and a and b are unknown constants. After the infinite time of inspection, the conflict reaches the equilibrium, which satisfies the equation, k(1 + ap*)n* = k(1 + bn*)p*. Here we define a parameter C, which is 2p*/[p*(1 - p*)]. After the infinite time of inspection, the conflict reaches the equilibrium, which satisfies t that changes in the confidence level with the time (dp/dt) is proportional to [k(1+ap)n - k(1+bn)p], i.e. k[-cp2 + (c - 2)p + 1]. Solving the differential equation, we derived the equation; t(p) and p(t) depending with the parameters; k, c, S. S (0-1) is the value arbitrary selected and related with probability of "abnormal" before the image inspection (S = p(0)). Image reading studies were executed for CT images. ROC curves were generated both by the traditional 4-step score-based method and by the confidence level; p estimated from the equation t(p) of the DDC model using observed judgment time. It was concluded that ROC curves could be generated by measuring time for dichotomous judgment without the subjective scores of diagnostic confidence and applying the DDC model.

An electrospray mass spectrometric method has been developed for application to agricultural and horticultural fertilizers to determine perchlorate. After fertilizers are leached or dissolved in water, the method relies on the formation of stable ion pair complex of the perchlor...

Nozzle contour data for untruncated Bell nozzles with expansion area ratios to 6100 and a specific heat ratio of 1.2 are provided. Curves for optimization of nozzles for maximum thrust coefficient within a given length, surface area, or area ratio are included. The nozzles are two dimensional axisymmetric and calculations were performed using the method of characteristics. Drag due to wall friction was included in the final thrust coefficient.

Exposure to malachite green (MG) may pose great health risks to humans; thus, it is of prime importance to develop fast and robust methods to quantitatively screen the presence of malachite green in water. Herein the application of extractive electrospray ionization mass spectrometry (EESI-MS) has been extended to the trace detection of MG within lake water and aquiculture water, due to the intensive use of MG as a biocide in fisheries. This method has the advantage of obviating offline liquid-liquid extraction or tedious matrix separation prior to the measurement of malachite green in native aqueous medium. The experimental results indicate that the extrapolated detection limit for MG was ~3.8 μg·L−1 (S/N = 3) in lake water samples and ~0.5 μg·L−1 in ultrapure water under optimized experimental conditions. The signal intensity of MG showed good linearity over the concentration range of 10–1000 μg·L−1. Measurement of practical water samples fortified with MG at 0.01, 0.1 and 1.0 mg·L−1 gave a good validation of the established calibration curve. The average recoveries and relative standard deviation (RSD) of malachite green in lake water and Carassius carassius fish farm effluent water were 115% (6.64% RSD), 85.4% (9.17% RSD) and 96.0% (7.44% RSD), respectively. Overall, the established EESI-MS/MS method has been demonstrated suitable for sensitive and rapid (<2 min per sample) quantitative detection of malachite green in various aqueous media, indicating its potential for online real-time monitoring of real life samples. PMID:27529262

Exposure to malachite green (MG) may pose great health risks to humans; thus, it is of prime importance to develop fast and robust methods to quantitatively screen the presence of malachite green in water. Herein the application of extractive electrospray ionization mass spectrometry (EESI-MS) has been extended to the trace detection of MG within lake water and aquiculture water, due to the intensive use of MG as a biocide in fisheries. This method has the advantage of obviating offline liquid-liquid extraction or tedious matrix separation prior to the measurement of malachite green in native aqueous medium. The experimental results indicate that the extrapolated detection limit for MG was ~3.8 μg·L(-1) (S/N = 3) in lake water samples and ~0.5 μg·L(-1) in ultrapure water under optimized experimental conditions. The signal intensity of MG showed good linearity over the concentration range of 10-1000 μg·L(-1). Measurement of practical water samples fortified with MG at 0.01, 0.1 and 1.0 mg·L(-1) gave a good validation of the established calibration curve. The average recoveries and relative standard deviation (RSD) of malachite green in lake water and Carassius carassius fish farm effluent water were 115% (6.64% RSD), 85.4% (9.17% RSD) and 96.0% (7.44% RSD), respectively. Overall, the established EESI-MS/MS method has been demonstrated suitable for sensitive and rapid (<2 min per sample) quantitative detection of malachite green in various aqueous media, indicating its potential for online real-time monitoring of real life samples. PMID:27529262

Molecular bioforensic research is dependent on rapid and sensitive methods such as real-time PCR (qPCR) for the identification of microorganisms. The use of synthetic positive control templates containing small modifications outside the primer and probe regions is essential to ensure all aspects of the assay are functioning properly, including the primers and probes. However, a typical qPCR or reverse transcriptase qPCR (qRT-PCR) assay is limited in differentiating products generated from positive controls and biological samples because the fluorescent probe signals generated from each type of amplicon are indistinguishable. Additional methods used to differentiate amplicons, including melt curves, secondary probes, and amplicon sequencing, require significant time to implement and validate and present technical challenges that limit their use for microbial forensic applications. To solve this problem, we have developed a novel application of electrospray ionization mass spectrometry (ESI-MS) to rapidly differentiate qPCR amplicons generated with positive biological samples from those generated with synthetic positive controls. The method has sensitivity equivalent to qPCR and supports the confident and timely determination of the presence of a biothreat agent that is crucial for policymakers and law enforcement. Additionally, it eliminates the need for time-consuming methods to confirm qPCR results, including development and validation of secondary probes or sequencing of small amplicons. In this study, we demonstrate the effectiveness of this approach with microbial forensic qPCR assays targeting multiple biodefense agents (bacterial, viral, and toxin) for the ability to rapidly discriminate between a positive control and a positive sample. PMID:23675878

Presented here is an analytical method to detect residual agar from a bacterial spore sample as an indication of culturing on an agar plate. This method is based on the resolubilization of agar polysaccharide from a bacterial spore sample, enzymatic digestion, followed by electrospray ionization tandem mass spectrometry (ESI-MSn) analysis for detection of a specific agar fragment ion. A range of Bacillus species and strains were selected to demonstrate the effectiveness of this approach. The characteristic agar fragment ion was detected in the spores grown on agar that were washed from 1 to 5 times, irradiated or non-irradiated and not in the spores grown in broth. A sample containing approximately 108 spores is currently needed for confident detection of residual agar from culture on agar plates in the presence of bacterial spores with a limit of detection of approximately 1 ppm agar spiked into a broth-grown spore sample. The results of a proficiency test with 42 blinded samples are presented demonstrating the utility of this method with no false positives and only 3 false negatives for samples that were below the detection level of the method as documented.

For identification of ginsenoside enantiomers, electrospray ionization mass spectrometry (ESI-MS) was used to generate silver complexes of the type [ginsenoside + Ag](+). Collision induced dissociation of the silver-ginsenoside complexes produced fragment ions by dehydration, allowing differentiation of ginsenoside enantiomers by the intensity of [M + Ag - H(2)O](+) ion. In the meanwhile, an approach based on the distinct profiles of enantiomer-selective fragment ion intensity varied with collision energy was introduced to refine the identification and quantitation of ginsenoside enantiomers. Five pairs of enantiomeric ginsenosides were distinguished and quantified on the basis of the distribution of fragment ion [M + Ag - H(2)O](+). This method was also extended to the identification of other type of ginsenoside isomers such as ginsenoside Rb2 and Rb3. For demonstrating the practicability of this novel approach, it was utilized to analyze the molar ratio of 20-(S) and 20-(R) type enantiomeric ginsenosides in enantiomer mixture in red ginseng extract. The generation of characteristic fragment ion [M + Ag - H(2)O](+) likely results from the reduction of potential energy barrier of dehydration because of the catalysis of silver ion. The mechanism of enantiomer identification of ginsenosides was discussed from the aspects of computational modeling and internal energy. PMID:23019162

Organophosphorus compounds have played important roles as pesticides, chemical warfare agents and extractors of radioactive material. Structural elucidation of phosphonates poses a particular challenge because their initial forms can be hydrolyzed, thus, degradation products may predominate in samples acquired in the field. The analysis of non-volatile organophosphorus compounds and their degradation products is possible using electrospray tandem mass spectrometry ESI-MS/MS. Here, we present a generic strategy that allows the unambiguous identification of substituents for two families of organophosphorus compounds: the phosphonates and phosphates. General fragmentation rules were deduced based on the study of decomposition pathways of 55 organophosphorus esters, including examples found in the literature. Multistage MS (MS(n)) experiments at high resolution in a hybrid mass spectrometer provide accurate mass measurements, whereas collision-induced dissociation experiments in a triple quadrupole give access to small fragment ions. The creation of a specific nomenclature for each possible structure of organophosphorus compound, depending on the alkyl side chain linked to the oxygen, was achieved by applying these fragmentation rules. This led to the creation of an 'identification tree' based upon the unique consecutive decomposition pathways uncovered for each individual compound. Hence, seven structural motifs were created that orient an unequivocal identification using the 'identification tree'. Despite the similar structures of the ensemble of phosphate and phosphonate esters, distinct identifications based upon characteristic neutral losses and diagnostic fragment ions were possible in all cases. PMID:23674282

Without any sample pretreatment, effervescent beverage fluids were manually sprayed into the primary ion plume created by using a nanoelectrospray ionization source for direct ionization, and the analyte ions of interest were guided into an ion trap mass spectrometer for tandem mass analysis. Functional ingredients (e.g., vitamins, taurine, and caffeine, etc.) and spiked impurity (e.g., cocaine) in various beverages, such as Red Bull energy drink, Coco-cola, and Pepsi samples were rapidly identified within 1.5 s. The limit of detection was found to be 7-15 fg (S/N = 3) for cocaine in different samples using the characteristic fragment (m/z 150) observed in the MS(3) experiments. Typical relative standard deviation and recovery of this method were 6.9%-8.6% and 104%-108% for direct analysis of three actual samples, showing that nanoextractive electrospray ionization tandem mass spectrometry is a useful technique for fast screening cocaine presence in beverages. PMID:19939702

Electrospray ionization (ESI) tandem mass spectrometry coupled with liquid chromatography is a routine technique for identifying and quantifying compounds in complex mixtures. The identification step can be aided by matching acquired tandem mass spectra (MS(2)) against reference library spectra as is routine for electron ionization (EI) spectra from gas chromatography/mass spectrometry (GC/MS). However, unlike the latter spectra, ESI MS(2) spectra are likely to originate from various precursor ions for a given target molecule and may be acquired at varying energies and resolutions and have characteristic noise signatures, requiring processing methods very different from EI to obtain complete and high quality reference spectra for individual analytes. This paper presents procedures developed for creating a tandem mass spectral library that addresses these factors. Library building begins by acquiring MS(2) spectra for all major MS(1) peaks in an infusion run, followed by assigning MS(2) spectra to clusters and creating a consensus spectrum for each. Intensity-based constraints for cluster membership were developed, as well as peak testing to recognize and eliminate suspect peaks and reduce noise. Consensus spectra were then examined by a human evaluator using a number of criteria, including a fraction of annotated peaks and consistency of spectra for a given ion at different energies. These methods have been developed and used to build a library from >9000 compounds, yielding 230,000 spectra. PMID:24896981

The ultraviolet aerodynamic particle sizer (UVAPS) spectrometer is a novel, commercially available aerosol counter for real-time, continuous monitoring of viable bioaerosols based on the fluorescence induced from living microorganisms. For aerosolization of liquid-based microorganisms, general aerosolization methods such as atomization or nebulization may not be adequate for an accurate and quantitative characterization of the microorganisms because of the formation of agglomerated particles. In such cases, biological electrospray techniques have an advantage because they generate nonagglomerated particles, attributable to the repulsive electrical forces among particles with unipolar charges. Biological electrosprays are quickly gaining potential for the detection and control of living organisms in applications ranging from mass spectrometry to developmental microbiology. In this study, we investigated the size distribution, total concentration, and fluorescence percentage of bacterial particles in a real-time manner by electrospray-assisted UVAPS. A suspension containing Escherichia coli as a test microorganism was sprayed in a steady cone-jet mode using a specially designed electrospray system with a point-to-orifice-plate configuration based on charge-reduced electrospray size spectrometry. With the electrospray process, 98% of the total E. coli particle number concentration had a size of <1 mum and the geometric mean diameter was 0.779 mum, as compared with the respective values of 78% and 0.907 mum after nebulization. The fractions of fluorescence responsive particles and of particles that contained viable organisms in culture were 12% and 7%, respectively, from the electrospray process and 34% and 24% from nebulization. These results demonstrate that (1) the presence of agglomerated particles can lead to markedly overestimated fluorescence and culturability percentages compared with the values obtained from nonagglomerated particles, and (2) electrospray

We are interested in clinical implications of adaptation to blurred and sharpened images. Therefore, we investigated repeatability, individual variability and characteristics of the adaptation curves in normally-sighted individuals (n=39). The point of subjective neutrality (PSN – the slope of the spatial spectrum of the image that appears normal) following adaptation was measured for each adaptation level and was used to derive individual adaptation curves for each subject. Adaptation curves were fitted with a modified Tukey biweight function as the curves were found to be tumbled-S shaped and asymmetrical for blur and sharp in some subjects. The adaptation curve was found to be an individual characteristic as inter-subject variability exceeds test-retest variability. The existence of individual variability may have implications for the prescription and clinical success of optical devices as well as image enhancement rehabilitation options. PMID:20417657

Recently, many papers have begun to consider so-called non-Quispel-Roberts-Thompson (QRT) birational maps of the plane. Compared to the QRT family of maps which preserve each biquadratic curve in a fibration of the plane, non-QRT maps send a biquadratic curve to another biquadratic curve belonging to the same fibration or to a biquadratic curve from a different fibration of the plane. In this communication, we give the general form of a birational map derived from a difference equation that sends a biquadratic curve to another. The necessary and sufficient condition for such a map to exist is that the discriminants of the two biquadratic curves are the same (and hence so are the j-invariants). The result allows existing examples in the literature to be better understood and allows some statements to be made concerning their generality.

In secondary electrospray ionization (SESI) systems, gaseous analytes exposed to an electrospray plume become ionized after charge is transferred from the charging electrosprayed particles (the charging agent) to the vapor species. Currently available SESI models are valid for simplified systems having only one type of electrosprayed species, which ionizes only one single vapor species, and for the limit of low vapor concentration. More realistic models require considering other effects. Here we develop a theoretical model that accounts for the effects of high vapor concentration, saturation effects, interferences between different vapor species, and electrosprays producing different types of species from the liquid phase. In spite of the relatively high complexity of the problem, we find simple relations between the different ionic species concentrations that hold independently of the particular ion source configuration. Our model suggests that an ideal SESI system should use highly concentrated charging agents composed preferably of only one dominating species with low mobility. Experimental measurements with a MeOH-H(2)O-NH(3) electrospray and a mixture of fatty acids and lactic acid served to test the theory, which gives good qualitative results. These results also suggest that the SESI ionization mechanism is primarily based on ions rather than on charged droplets. PMID:22528202

We provide a thorough characterization of the low-flow electrospray as an ionization source for mass spectrometry (MS) using solutions typical for reversed-phase liquid chromatography. As expected, the electrospray operating regime strongly affects the MS signal; however, contrary to conventional wisdom, the pulsating regime consistently offers better performance than the cone-jet regime in these experimental conditions. We explain this observation by a highly efficient ionization achieved by the pulsating electrospray at low flow rates, rendering the increased charge generated by a cone-jet electrospray detrimental for transmission from atmospheric pressure to vacuum through a heated capillary interface. Over a wide range of voltages, the pulsating electrospray provides a relatively constant MS signal intensity, which depends significantly on the distance between the emitter and the MS inlet. For cone-jet electrosprays the MS signal decreases slightly with increasing voltage, but the signal is less affected by the emitter-inlet distance. At flow rates up to 100 nL/min the MS signal increases with increasing flow rate due to the larger number of ions supplied into the gas phase. At flow rates greater than 100 nL/min, the signal reaches a plateau due to increasingly unsatisfactory ionization efficiency at larger flow rates.

In recent years, electrophoretic deposition (EPD) has been adopted as a cost-effective and reliable single-step solution-based room temperature coating method for carbon nanotubes (CNTs), predominantly on conducting surfaces. Contrary to this general pre-requisite of conductive target substrates, in this work we have explored a fabrication strategy for the scalable deposition of CNTs on insulating glass surfaces by the sequential combination of electrospraying and the EPD technique. This combined process flow has been referred to as "electrospray-assisted EPD", where an initial CNT coating on glass substrates is obtained by electrospraying which, in turn, further assists CNT film growth by EPD. The successful integration of the electrospray technique in the EPD process flow also eliminates the need for surface functionalization of the insulator substrates prior to the deposition step. Electrospray-assisted EPD has resulted in the successful fabrication of uniform, homogenous, and thick CNT deposits (˜4.5 - 5 μm) with precise thickness control. A detailed investigation of the effect of the initial electrosprayed coating on the final CNT film growth and thickness is also presented in this report. This research endeavor presents a significant opportunity for the integration of this deposition model into a wider platform of materials research and technology, chemical sensing, and applications based upon printable and flexible electronics. [Figure not available: see fulltext.

The performance of electrosprayed cathode catalyst layers in a polymer electrolyte membrane fuel cell (PEMFC) is studied using a localized reference electrode technique. Single cells with an electrosprayed cathode catalyst layer show an increase of >20% in maximum power density under standard testing conditions, compared with identical cells assembled with a conventional, state-of-the-art, gas diffusion cathode. When operated at high current density (1.2 A cm-2) the electrosprayed catalyst layers show more homogeneous distribution of the localized cathode potential, with a standard deviation from inlet to outlet of <50 mV, compared with 79 mV for the conventional gas diffusion cathode. Higher performance and homogeneity of cell response is attributed to the superhydrophobic nature of the macroporous electrosprayed catalyst layer structure, which enhances the rate of expulsion of liquid water from the cathode. On the other hand, at low current densities (<0.5 A cm-2), the electrosprayed layers exhibit more heterogeneous distribution of cathode potential than the conventional cathodes; this behavior is attributed to less favorable kinetics for oxygen reduction in very hydrophobic catalyst layers. The optimum performance may be obtained with electrosprayed catalyst layers employing a high Pt/C catalyst ratio.

Biodegradable poly (lactic-co-glycolic acid) (PLGA) microparticles are an effective way to achieve sustained drug release. In this study, we investigated a sustained release model of PLGA microparticles with incorporated protein via either emulsion or coaxial electrospray techniques. PLGA (75:25) was used as the carrier, and bovine serum albumin as a model protein. Coaxial electrospray resulted in a type of core–shell structure with mean diameters of 2.41 ± 0.60 µm and a centralised protein distribution within the core. Emulsion electrospray formed bigger microparticles with mean diameters of 22.75 ± 8.05 µm and a heterogeneous protein distribution throughout the microparticles. The coaxial electrospray microparticles presented a much slighter burst release than the emulsion electrospray microparticles. Loading efficiency was significantly higher (p electrospray could produce protein-loaded microparticles with sustained release behaviour, but the former revealed a superior approach for drug delivery. PMID:23346923

A novel electrospray setup was found effective for direct analysis of fullerene solutions by electrospray (ES) mass spectrometry. The electrospray capillary needle used for the analysis is equipped with a thin metal (copper, platinum or stainless steel) wire installed inside the capillary. The wire tip protrudes slightly from the capillary end. In this configuration the high electrical field formed by the wire tip stimulates a specific electrospray mode with a fine spray originating from the tip. The correlation of the acquired mass spectra with the magnified view of the spray at the capillary tip was investigated. The effective formation of fullerene ions in both negative and positive ion modes was observed in mass spectra only in the specific case of the electrospray originating from the wire tip. The fullerene di-anions observed in the negative ES mass spectra provide evidence for the electrochemical nature of this process occurring at the ES capillary tip. Observation of fullerene ions in mass spectra obtained using the suggested electrospray arrangement is assumed to be a consequence of the fine spray originating from the sharp metal wire tip. In this case the liquid/metal interface is near the Taylor cone apex. PMID:15052560

The fragmentation patterns of a series of dispirocyclopiperazinium dibromides with strong analgesic activity were analyzed by positive ion electrospray ionization mass spectrometry in conjunction with tandem mass spectrometry (ESI-MSn). The [C2+Br-]+ ions showed the characteristic isotopic peaks with high intensity. In each of their MS2 spectra, only the [C2+Br----HBr]+ ion peak was observable. Further analysis indicated that a selective rearrangement occurred in the unsaturated spirocyclopiperazine ring to achieve dihydropyrrole moiety. Meanwhile, the [C]2+ ions were unique and always the base peaks. The ions [C2+Br-]+ and [C]2+ were formed from the equilibrium of precursor molecules 1 in solution, and the latter ions could not be observed in the MS2 spectra of ions [C2+Br-]+. The related fragmentation mechanisms were proposed.

Wet process of soluble organic light emitting diode (OLED) materials has attracted much attention due to its potential as a large-area manufacturing process with high productivity. Electrospray (ES) deposition is one of candidates of organic thin film formation process for OLED. However, to fabricate red, green, and blue emitters for color display, a fine metal mask is required during spraying emitter materials. We demonstrate a mask-less color pixel patterning process using ES of soluble OLED materials and selective biasing on pixel electrodes and a spray nozzle. We show red and green line patterns of OLED materials. It was found that selective patterning can be allowed by coulomb repulsion between nozzle and pixel. Furthermore, we fabricated blue fluorescent OLED devices by vacuum evaporation and ES processes. The device performance of ES processed OLED showed nearly identical current-voltage characteristics and slightly lower current efficiency compared to vacuum processed OLED.

Two insecticides, diflubenzuron and hexaflumuron, and their analogs have been separated by liquid chromatography (LC) and their fragmentation mechanisms were studied by electrospray ionization-ion trap mass spectrometry (ESI-MS(n)) in both positive- and negative-ion modes. Sequential product ion fragmentation experiments were performed in order to explain the degradation pathways and identify their predominant fragment ions. It was indicated that the characteristic fragmentations are the loss of neutral molecules such as HF, HNO(2), and HCl to form stable ring structure or the cleavage of the acyl amine to form conjugated structure. Furthermore, the separation and determination of two benzoylurea (BU) insecticides and their analogs in the water samples from Weiming Lake have been described by LC-ESI-MS in negative mode. By the use of deprotonated molecule for quantitative analysis at low capillary exit voltage, low detection limits, good linearity and reproducibility for standard solutions were presented. PMID:18970732

Quantitative determination of caffeine on reversed-phase C8 thin-layer chromatography plates using a surface sampling electrospray ionization system with tandem mass spectrometry detection is reported. The thin-layer chromatography/electrospray tandem mass spectrometry method employed a deuterium-labeled caffeine internal standard and selected reaction monitoring detection. Up to nine parallel caffeine bands on a single plate were sampled in a single surface scanning experiment requiring 35 min at a surface scan rate of 44 {mu}m/s. A reversed-phase HPLC/UV caffeine assay was developed in parallel to assess the mass spectrometry method performance. Limits of detection for the HPLC/UV and thin-layer chromatography/electrospray tandem mass spectrometry methods determined from the calibration curve statistics were 0.20 ng injected (0.50 {mu}L) and 1.0 ng spotted on the plate, respectively. Spike recoveries with standards and real samples ranged between 97 and 106% for both methods. The caffeine content of three diet soft drinks (Diet Coke, Diet Cherry Coke, Diet Pepsi) and three diet sport drinks (Diet Turbo Tea, Speed Stack Grape, Speed Stack Fruit Punch) was measured. The HPLC/UV and mass spectrometry determinations were in general agreement, and these values were consistent with the quoted values for two of the three diet colas. In the case of Diet Cherry Coke and the diet sports drinks, the determined caffeine amounts using both methods were consistently higher (by 8% or more) than the literature values.

Electrospray is a soft ionization technique commonly used to charge large biomolecules; it has, however, also been applied to inorganic compounds. We are extending this technique to mineral microparticles. Electrospray-charged mineral microparticles are interesting in the context of surface science because surface chemistry dictates where and how charge carriers can bond to mineral surfaces. In addition, using electrospray to charge mineral particles allows these particles to be electrostatically accelerated as projectiles in high- and hyper-velocity impacts. Since current techniques for producing high- and hyper-velocity microparticle impacts are largely limited to metal or metal-coated projectiles, using minerals as projectiles is a significant innovation. Electrospray involves three steps: creation of charged droplets containing solute/particles, evaporation and bifurcation of droplets, and desolvation of the solute/particles. An acidified solution is slowly pumped through a needle in a strong DC field, which causes the solution to break into tiny, charged droplets laden with protons. Solvent evaporates from the electrosprayed droplets as they move through the electric field toward a grounded plate, causing the charge on the droplet to increase relative to its mass. When the electrosprayed droplet’s charge becomes such that the droplet is no longer stable, it bifurcates, and each of the resulting droplets carries some of the original droplet’s charge. Evaporation and bifurcation continues until the solute particle is completely desolvated. The result is a protonated solute molecule or particle. We built an instrument that electrosprays particles into vacuum and measures them using an image charge detector. Mineral microparticles were prepared by grinding natural mineral samples to ~2 µm diameter. These microparticles are then added to a 4:1 methanol:water solution to create a 0.005% w/v suspension. The suspension is electrosprayed into vacuum, where the

Electrospray mass spectrometry (ES-MS) is one of the more widely used analysis methods in science today, impacting fields as diverse as conventional chemistry to biotechnology and materials science. , Even 20 years after bursting onto the mass spectrometry scene, the underlying processes in ES ionization continue to be better understood exposing new opportunities for the technique. , , , , Such is the case for the improved understanding related to the electrochemical processes inherent to the operation of this ion source, , , which is the topic of this report. Electrospray ionization involves three main steps prior to mass analysis: the generation and charging of the ES droplets; droplet evaporation and the production of gas-phase ions; and secondary processes that modify the gas-phase ions in the atmosphere and the sub-atmospheric pressure sampling regions of the mass spectrometer. Integral to the generation and charging of the ES droplets are electrochemical reactions that occur at the conductive contact/solution interface within or near the ES emitter to maintain the quasi-continuous production of charged droplets and ultimately gas-phase ions. The basic electrochemical phenomena concerning the ES ion source were first brought to wide attention in the mass spectrometry community by Kebarle and co-workers in the early 1990's,8 but the electrochemistry of electrostatic spray devices and possible analytical consequences resulting from this phenomenon were realized and discussed in the literature at least as far back as the mid-1970's. When asked to intercede in a debate on the significance of electrochemistry in the ES ionization (ESI) process, 2002 Nobel Laureate in Chemistry John Fenn noted that to him " the idea that electrochemical reactions might be taking place in an ES ion source was too obvious to mention. That products of such reactions are of vital significance in the overall ESI process was much less obvious. Indeed, it seems fair to say that with few

We describe a method to perform scalar multiplication on two classes of ordinary elliptic curves, namely E:y2=x3+Ax in prime characteristic p≡1mod4, and E:y2=x3+B in prime characteristic p≡1mod3. On these curves, the 4-th and 6-th roots of unity act as (computationally efficient) endomorphisms. In order to optimise the scalar multiplication, we consider a width-w-NAF (Non-Adjacent Form) digit expansion of positive integers to the complex base of τ, where τ is a zero of the characteristic polynomial x2−tx+p of the Frobenius endomorphism associated to the curve. We provide a precomputationless algorithm by means of a convenient factorisation of the unit group of residue classes modulo τ in the endomorphism ring, whereby we construct a digit set consisting of powers of subgroup generators, which are chosen as efficient endomorphisms of the curve. PMID:25190900

The receiver operating characteristic (ROC) curve has been widely used as an evaluation criterion to measure the accuracy of biometrics system. Unfortunately, such an ROC curve provides no indication of the optimum threshold and cost function. In this paper, two kinds of 3D combinational curves are proposed: the 3D combinational accuracy curve and the 3D combinational performance curve. The 3D combinational accuracy curve gives a balanced view of the relationships among FAR (false alarm rate), FRR (false rejection rate), threshold t, and Cost. Six 2D curves can be derived from the 3D combinational accuracy curve: the conventional 2D ROC curve, 2D curve of (FRR, t), 2D curve of (FAR, t), 2D curve of (FRR, Cost), 2D curve of (FAR, Cost), and 2D curve of ( t, Cost). The 3D combinational performance curve can be derived from the 3D combinational accuracy curve which can give a balanced view among Security, Convenience, threshold t, and Cost. The advantages of using the proposed 3D combinational curves are demonstrated by iris recognition systems where the experimental results show that the proposed 3D combinational curves can provide more comprehensive information of the system accuracy and performance.

An amplitude correlation between the pulsation velocity curves and visual light curves of ab-type RR Lyrae stars is derived from a large number of RR Lyrae that have high-precision radial-velocity and photometric data. Based on the determined AVp, AV ralation, a synthetic radial-velocity curve for a typical ab-type RR Lyrae star is constructed. This would be of particular use in determining the systemic velocities of RR Lyrae. 17 refs.

A beam of electrosprayed nanodroplets impacting on single-crystal silicon amorphizes a thin surface layer of a thickness comparable to the diameter of the drops. The phase transition occurs at projectile velocities exceeding a threshold, and is caused by the quenching of material melted by the impacts. This article demonstrates that the amorphization of silicon is a general phenomenon, as nanodroplets impacting at sufficient velocity also amorphize other covalently bonded crystals. In particular, we bombard single-crystal wafers of Si, Ge, GaAs, GaP, InAs, and SiC in a range of projectile velocities, and characterize the samples via electron backscatter diffraction and transmission electron microscopy to determine the aggregation state under the surface. InAs requires the lowest projectile velocity to develop an amorphous layer, followed by Ge, Si, GaAs, and GaP. SiC is the only semiconductor that remains fully crystalline, likely due to the relatively low velocities of the beamlets used in this study. The resiliency of each crystal to amorphization correlates well with the specific energy needed to melt it except for Ge, which requires projectile velocities higher than expected.

In this study, we developed a novel electrospray ionization (ESI) technique based on household aluminum foil (Al foil) and demonstated the desirable features and applications of this technique. Al foil can be readily cut and folded into desired configuration for effective ionization and for holding sample solution in bulk to allowing acquisition of durable ion signals. The present technique was demonstrated to be applicable in analysis of a wide variety of samples, ranging from pure chemical and biological compounds, e.g., organic compounds and proteins, to complex samples in liquid, semi-solid, and solid states, e.g., beverages, skincare cream, and herbal medicines. The inert, hydrophobic and impermeable surface of Al foil allows convenient and effective on-target extraction of solid samples and on-target sample clean-up, i.e., removal of salts and detergents from proteins and peptides, extending ESI device from usually only for sample loading and ionization to including sample processing. Moreover, Al foil is an excellent heat-conductor and highly heat-tolerant, permitting direct monitoring of thermal reactions, e.g., thermal denaturation of proteins. Overall, the present study showed that Al-foil ESI could be an economical and versatile method that allows a wide range of applications. PMID:24594810

A new single-capillary electrospray (ES) aerosol generator has been developed for monodisperse particle production with maximal transmission efficiency. The new generator consists of both a spray chamber in a point-to-orifice-plate configuration and a charge reduction chamber that can hold up to 4 Nuclespot ionizers (Model P-2042, NRD Inc.). The 2 chambers are partitioned by an orifice plate. To optimize the particle transmission efficiency of the prototype, a systematic study was performed on the generator by varying the system setup and operation. Two key dimensions of the generator setup, the orifice diameter and the distance from the capillary tip to the orifice plate, were varied. Fluorescence analysis was applied to characterize the loss of ES-generated particles at different locations of the prototype. It was found that particle loss in the generator could be reduced by either increasing the orifice diameter or decreasing the distance between the capillary tip and the orifice plate. Increasing either the total radioactivity of the ionizers or the flowrate of the particle carrier gas also further decreased the particle loss in the system. The maximum particle transmission efficiency of 88.0% was obtained with the spray chamber fully opened to the charge reduction chamber, the capillary tip at the same level as the orifice plate, and 4 bipolar ionizers installed. PMID:22829715

Electrospray ionization (ESI) is a widely adopted soft ionization method for mass spectroscopy (MS). In spite of the undeniable success of the technique, its mechanisms are difficult to be analytically modelled because the process is characterized by non-equilibrium conditions. The common belief is that the formation of gas-phase ions takes place at the apex of the Taylor cone via electrophoretic charging. The charge balance implies that a conversion of electrons to ions should occur at the metal-liquid interface of the injector needle. We have detected that the above description is based on unproved assumptions which are not consistent with the correct evaluation of the problem. The comparison between experiments performed under the usual geometry and observations obtained under symmetric field configurations suggests that the emitted droplets cannot be significantly charged or, at least, that any possible ionization mechanism is so poorly efficient to ensure that columbic forces cannot play a major role in jet formation, even in cases where the liquid consists of a solution of ionic species. Further work is required to clearly understand how ionization occurs in ESI-MS.

The influence of instrumental parameters affecting the ionization in continuous full filling capillary electrochromatography/electrospray ionization mass spectrometry (CFF-CEC/ESI-MS) was investigated. The investigated parameters were the BGE and sheath liquid ion strength and organic modifier content, the nebulizer gas pressure, and the concentration of nanoparticles in the BGE. It was found that the nebulizer pressure had the largest influence on the separation efficiency and apparent retention. It was shown that even the lowest pressure investigated was sufficient to guide the nanoparticle flow away from the mass spectrometer inlet. A nebulizer pressure of 5 psi was found to be optimal; increasing the pressure significantly decreased the separation efficiency due to the generation of a hydrodynamic flow. Generally, the ion strength of both the BGE and the sheath liquid were found to have very moderate effects on the separation of a homologous series of dialkyl phthalates, whereas the ionization efficiency was found to be unaffected by the nanoparticles and the separation efficiency was found to increase with increasing concentrations up to 3.8 mg/mL, whereafter it was observed to drop. The optimized method was linear over a wide concentration range and presented LOD and LOQ more than threefold lower than those previously reported using CFF-CEC/ESI-MS. PMID:21254124

Electrospinning is a widely established polymer-processing technology that allows generation of fibers (in nanometer to micrometer size) that can be collected to form nonwoven structures. By choosing suitable process parameters and appropriate solvent systems, fiber size can be controlled. Since the technology allows the possibility of tailoring the mechanical properties and biological properties, there has been a significant effort to adapt the technology in tissue regeneration and drug delivery. This review focuses on recent developments in adapting this technology for tissue regeneration applications. In particular, different configurations of nozzles and collector plates are summarized from the view of cell seeding and distribution. Further developments in obtaining thick layers of tissues and thin layered membranes are discussed. Recent advances in porous structure spatial architecture parameters such as pore size, fiber size, fiber stiffness, and matrix turnover are summarized. In addition, possibility of developing simple three-dimensional models using electrosprayed fibers that can be utilized in routine cell culture studies is described. PMID:21210761

Anti-VEGF therapies have been widely explored for the management of posterior ocular disease, like neovascular age-related macular degeneration (AMD). Loading anti-VEGF therapies in biodegradable microparticles may enable sustained drug release and improved therapeutic outcome. However, existing microfabrication processes such as double emulsification produce drug-loaded microparticles with low encapsulation rate and poor antibody bioactivity. To overcome these limitations, we fabricate multifunctional microparticles by both single needle and coaxial needle electrospray. The experimental setup for the process includes flat-end syringe needles (both single needle and coaxial needle), high voltage power supplies, and syringe pumps. Microparticles are formed by an electrical field between the needles and the ground electrode. Droplet size and morphology are controlled by multiple process parameters and material properties, such as flow rate and applied voltage. The droplets are collected and freezing dried to obtain multifunctional microparticles. Fluorescent beads encapsulated poly(DL-lactide-co-glycolide) acid (PLGA) microparticles are injected into rabbits eyes through intravitreal injection to test the biodegradable time of microparticles.

Nan-fiber scaffolds are suitable tools for tissue engineering. Electro spinning materials together with cells presents not adequate to obtain a high cellular zing tissue constructs as the shear force, tensile force, and other physical effects excited in the electro spinning process, which are harmful to cellular differentiation, development and function. However, this limitation has been overcome by a micro integration system of simultaneously bio-electro spraying human adipose stem cells (ASCs) and electro spinning Polyvinyl alcohol (PVA). Then it was compared to the single electro spinning nan-fiber scaffolds in relation to cell viability, which showed that the scaffolds by micro integration approach has a larger number of surviving cells and more suitable for cell growth and proliferation. In addition, the relationship between different parameters of biological electrospray (voltage, flow rate and distance of the needle from the collecting board) and droplet size of cell suspension was elucidated and the droplets with a near-mono distribution (<50um) could be generated to deposit a single living cell within a droplet. The association of bio-electro spraying with electro spinning (a scaffold preparation technique) has been demonstrated to be a promising and suitable tissue engineering approach in producing nan-fiber based three-dimensional (3-D) cell seeded scaffolds. PMID:26089992

High-frequency (>10 kHz) ac electrospray is shown to eject volatile dielectric liquid drops by an entirely different mechanism from dc sprays. The steady dc Taylor conic tip is absent and continuous spraying of submicron drops is replaced by individual dynamic pinchoff events involving the entire drop. We attribute this spraying mechanism to a normal Maxwell force produced by an undispersed plasma cloud in front of the meniscus that produces a visible glow at the spherical tip. The volume charge within the cloud is formed by electron-induced gas ionization of the evaporated liquid and produces a large normal field that is much higher than the nominal applied field such that drop ejection occurs at a voltage (at high frequencies) that is as much as ten times lower than that for dc sprays. The ejection force is sensitive to the liquid properties (but not its electrolyte composition), the ac frequency and trace amounts of inert gases, which are believed to catalyze the ionization reactions. As electroneutral drops are ejected, due to the large (>100) ratio between individual drop ejection time and the ac frequency, this mechanism can produce large (microns) electroneutral drops at relatively low voltages.

Quaternary ammonium salts (Quats) and amines are known to facilitate the MS analysis of high molar mass polyethers by forming low charge state adduct ions. The formation, stability, and behavior upon collision-induced dissociation (CID) of adduct ions of polyethers with a variety of Quats and amines were studied by electrospray ionization quadrupole time-of-flight, quadrupole ion trap, and linear ion trap tandem mass spectrometry (MS/MS). The linear ion trap instrument was part of an Orbitrap hybrid mass spectrometer that allowed accurate mass MS/MS measurements. The Quats and amines studied were of different degree of substitution, structure, and size. The stability of the adduct ions was related to the structure of the cation, especially the amine's degree of substitution. CID of singly/doubly charged primary and tertiary ammonium cationized polymers resulted in the neutral loss of the amine followed by fragmentation of the protonated product ions. The latter reveals information about the monomer unit, polymer sequence, and endgroup structure. In addition, the detection of product ions retaining the ammonium ion was observed. The predominant process in the CID of singly charged quaternary ammonium cationized polymers was cation detachment, whereas their doubly charged adduct ions provided the same information as the primary and tertiary ammonium cationized adduct ions. This study shows the potential of specific amines as tools for the structural elucidation of high molar mass polyethers.

Summary Large organic molecules are of important interest for organic-based devices such as hybrid photovoltaics or molecular electronics. Knowing their adsorption geometries and electronic structures allows to design and predict macroscopic device properties. Fundamental investigations in ultra-high vacuum (UHV) are thus mandatory to analyze and engineer processes in this prospects. With increasing size, complexity or chemical reactivity, depositing molecules by thermal evaporation becomes challenging. A recent way to deposit molecules in clean conditions is Electrospray Ionization (ESI). ESI keeps the possibility to work with large molecules, to introduce them in vacuum, and to deposit them on a large variety of surfaces. Here, ESI has been successfully applied to deposit triply fused porphyrin molecules on an insulating KBr(001) surface in UHV environment. Different deposition coverages have been obtained and characterization of the surface by in-situ atomic force microscopy working in the non-contact mode shows details of the molecular structures adsorbed on the surface. We show that UHV-ESI, can be performed on insulating surfaces in the sub-monolayer regime and to single molecules which opens the possibility to study a variety of complex molecules. PMID:26665062

Mass spectrometry imaging (MSI) provides untargeted molecular information with the highest specificity and spatial resolution for investigating biological tissues at the hundreds to tens of microns scale. When performed under ambient conditions, sample pre-treatment becomes unnecessary, thus simplifying the protocol while maintaining the high quality of information obtained. Desorption electrospray ionization (DESI) is a spray-based ambient MSI technique that allows for the direct sampling of surfaces in the open air, even in vivo. When used with a software-controlled sample stage, the sample is rastered underneath the DESI ionization probe, and through the time domain, m/z information is correlated with the chemical species' spatial distribution. The fidelity of the DESI-MSI output depends on the source orientation and positioning with respect to the sample surface and mass spectrometer inlet. Herein, we review how to prepare tissue sections for DESI imaging and additional experimental conditions that directly affect image quality. Specifically, we describe the protocol for the imaging of rat brain tissue sections by DESI-MSI. PMID:23892773

Electrohydrodynamic (EHD) techniques refer to procedures that utilize electrostatic forces to fabricate fibers or particles of different shapes with sizes in the nano-range to a few microns through electrically charged fluid jet. Employing different techniques, such as blending, surface modification, and coaxial process, there is a great possibility of incorporating bioactive such molecules as drugs, DNA, and growth factors into the nanostructures fabricated via EHD techniques. By careful selection of materials and processing conditions, desired encapsulation efficiency as well as preserved bioactivity of the therapeutic agents can be achieved. The drug-loaded nanostructures produced can be applied via different routes, such as implantation, injection, and topical or oral administration for a wide range of disease treatment. Taking advantage of the recent developments in EHD techniques like the coaxial process or multilayered structures, individually controlled delivery of multiple drugs is achievable, which is of great demand in cancer therapy and growth-factor delivery. This review summarizes the most recent techniques and postmodification methods to fabricate electrospun nanofibers and electrosprayed particles for drug-delivery applications. PMID:23976851

We report a novel ion-pair chromatography (IPC) approach for liquid chromatography electrospray ionization mass spectrometry (LC-ESI-MS), where the eluent does not contain any ion-pairing reagent (IPR). The IPR is injected on the column, much like the sample, and moves down the column. Significant amounts of a high retention factor IPR is injected, resulting in a transient but reproducible regional coating that progresses along the column. The sample is injected after a brief interval. The sample components interact with the IPR coated region during their passage; the chosen eluent gradient elutes the analytes of interest into the mass spectrometer before the IPR. Following analyte elution, the gradient is steeply raised, the IPR is washed out, and the effluent is sent to waste via a diverter valve until it is fully removed. As the nature of the analyte retention continuously changes along the column and with time, we call this transient ion-pair separation (TIPS). As the IPR never enters the MS, TIPS addresses two major drawbacks of IPC for ESI-MS: it avoids both ion suppression and ion source contamination. The potential of the generic approach for other modes of separation is discussed. An illustrative separation of two small inorganic ions, iodate and nitrate, is demonstrated on a reverse phase column by a transient prior injection of hexadecyltrimethylammonium chloride as IPR. PMID:26765166

Nowdays, one of the most challenges for the researchers is the formulation of poorly water soluble drugs. Reduction of particle size of active agents to submicron range could result in a faster dissolution rate and higher bioavailability. Integration as crystallization process is an often used particle size decreasing technique. The aim of this study was to show the theoretical background and practical application of the electros pray crystallization as an innovative particle size decreasing technique. Our model drug was the niflumic acid (NIF), which belongs to the BCS Class II. After the optimization of the process parameters, the physico-chemical properties of the samples were characterized. Particle size and shape were visualized by scanning electron microscopy (SEM). Crystalline state of NIF and the samples were investigated using differential scanning calorimetry (DSC) and X-ray powder diffraction. Physico-chemical properties were determined using dissolution test from simulated media. The electrospray crytallization resulted in particle size reduction but the aggregation of nanonized NIF crystals (NIF-nano) could not avoid without excipient. Aggregates with poor secondary forces are suitable for production of the interactive physical mixture. It was found that NIF-nano could be well distributed on the surface of the mannitol as carrier and the Poloxamer R protected the NIF-nano crystals (320 nm)from aggregation. Consequently, the physical mixture resulted in product with higher polarity, better wettability and faster dissolution rate of NIF as raw NIF or NIF-nano. PMID:26390735

4-Carboxybenzensulfonamide-chitosan (4-CBS-chitosan) microspheres were prepared by electrospraying with acetazolamide (ACZ) as a model drug. The obtained 4-CBS-chitosan microspheres with or without ACZ-loading were characterized by Fourier transform infrared spectroscopy, differential scanning colorimetry, scanning electron microscopy and particle size analyses. The crystalline form and the stability of ACZ in a basic solution was determined using X-ray single crystal analysis. 4-CBS-chitosan had 90% encapsulation efficiency for ACZ compared to 47% of encapsulation efficiency (EE) obtained from native chitosan, forming 3.1 μm diameter microspheres with a low polydispersity index (0.4). After an initial burst release (58% in 5 min), ACZ-loaded 4-CBS-chitosan gave a sustained release of ACZ (∼ 100% over 3h) in simulated gastric fluid (0.1N HCl; pH 1.2), which was better than that seen for the release from ACZ-loaded chitosan (44% over 1.5h). Thus, 4-CBS-chitosan microspheres are a possible drug carrier in acidic conditions, such as at the gastric mucosal wall. PMID:24360896

A new single-capillary electrospray (ES) aerosol generator has been developed for monodisperse particle production with maximal transmission efficiency. The new generator consists of both a spray chamber in a point-to-orifice-plate configuration and a charge reduction chamber that can hold up to 4 Nuclespot ionizers (Model P-2042, NRD Inc.). The 2 chambers are partitioned by an orifice plate. To optimize the particle transmission efficiency of the prototype, a systematic study was performed on the generator by varying the system setup and operation. Two key dimensions of the generator setup, the orifice diameter and the distance from the capillary tip to the orifice plate, were varied. Fluorescence analysis was applied to characterize the loss of ES-generated particles at different locations of the prototype. It was found that particle loss in the generator could be reduced by either increasing the orifice diameter or decreasing the distance between the capillary tip and the orifice plate. Increasing either the total radioactivity of the ionizers or the flowrate of the particle carrier gas also further decreased the particle loss in the system. The maximum particle transmission efficiency of 88.0% was obtained with the spray chamber fully opened to the charge reduction chamber, the capillary tip at the same level as the orifice plate, and 4 bipolar ionizers installed. PMID:22829715

From 2000 through 2011, there were 14 criminal cases of violations of the Clean Water Act involving the discharge of chromium, a toxic heavy metal, into drinking and surface water sources. As chromium(VI), a potential carcinogen present in the environment, represents a significant safety concern, it is currently the subject of an EPA health risk assessment. Therefore, sensitive and selective detection of this species is highly desired. This study reports the analysis of chromium(VI) in water samples by electrospray ionization mass spectrometry (ESI-MS) following its reduction and complexation with ammonium pyrrolidinedithiocarbamate (APDC). The reduction and subsequent complexation produce a characteristic [Cr(III)O]-PDC complex which can be detected as a protonated ion of m/z 507 in the positive ion mode. The detection is selective to chromium(VI) under acidic pH, even in the presence of chromium(III) and other metal ions, providing high specificity. Different water samples were examined, including deionized, tap, and river waters, and sensitive detection was achieved. In the case of deionized water, quantification over the concentration range of 3.7 to 148ppb gave an excellent correlation coefficient of 0.9904 using the enhanced MS mode scan. Using the single-reaction monitoring (SRM) mode (monitoring the characteristic fragmentation of m/z 507 to m/z 360), the limit of detection (LOD) was found to be 0.25ppb. The LOD of chromium(VI) for both tap and river water samples was determined to be 2.0ppb. A preconcentration strategy using simple vacuum evaporation of the aqueous sample was shown to further improve the ESI signal by 15 fold. This method, with high sensitivity and selectivity, should provide a timely solution for the real-world analysis of toxic chromium(VI). PMID:23937937

Light extraction blocks, and OLED lighting panels using light extraction blocks, are described, in which the light extraction blocks include various curved shapes that provide improved light extraction properties compared to parallel emissive surface, and a thinner form factor and better light extraction than a hemisphere. Lighting systems described herein may include a light source with an OLED panel. A light extraction block with a three-dimensional light emitting surface may be optically coupled to the light source. The three-dimensional light emitting surface of the block may includes a substantially curved surface, with further characteristics related to the curvature of the surface at given points. A first radius of curvature corresponding to a maximum principal curvature k.sub.1 at a point p on the substantially curved surface may be greater than a maximum height of the light extraction block. A maximum height of the light extraction block may be less than 50% of a maximum width of the light extraction block. Surfaces with cross sections made up of line segments and inflection points may also be fit to approximated curves for calculating the radius of curvature.

Using Voyager observations, it is demonstrated that Triton's orbital light curve is strongly wavelength-dependent, a characteristic which readily explains some of the apparent discrepancies among pre-Voyager telescopic measurements. Specifically, a light curve amplitude (peak to peak) is found that decreases systematically with increasing wavelength from about 0.08 magnitude (peak to peak) near 200 nm to less than 0.02 magnitude near 1000 nm. Peak brightness occurs near 90 deg orbital longitude (leading hemisphere). The brightness variation across this hemisphere is close to sinusoidal; the variation across the darker hemisphere is more complex. The decrease in light curve amplitude with increasing wavelength appears to be due to a decrease in contrast among surface markings, rather than to atmospheric obscuration. The model also explains the observed decrease in the amplitude of Triton's light curve at visible wavelengths over the past decade, a decrease related to the current migration of the subsolar latitude toward the south pole; it is predicted that this trend will continue into the 1990s.

A sensitive and specific liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) method was developed and validated for the identification and quantification of voriconazole (VRC, CAS 137234-62-9) in human plasma. Following liquid-liquid extraction, VRC and loratadine (internal standard, CAS 79794-75-5) were separated using a mobile phase comprised of methanol: water (0.1% formic acid) = 75:25 v/v on a Shimadzu Shim-pack VP-ODS C18 (150 x 2.0 mm ID, 5 microm) column and analyzed by electrospray ionization mass spectrometry. The chromatographic separation was achieved in less than 6 min. The standard curves were linear (r = 0.9994) over the concentration range of 2-2000 ng/mL for VRC and had good accuracy and precision. Both intra- and inter-batch standard deviations were less than 15%. The method was successfully applied to study the comparative bioavailability of VRC tablets test vs. reference in healthy Chinese volunteers through the statistical comparison of pharmacokinetic parameters obtained with the two formulations. PMID:21428249

A new high pressure liquid chromatography-electrospray ionization-tandem mass spectrometry method for the simultaneous determination of glucosinolates, as glucoraphanin and glucoerucin, and the corresponding isothiocyanates, as sulforaphane and erucin, was developed and applied to quantify these compounds in Eruca sativa defatted seed meals and enriched functional foods. The method involved solvent extraction, separation was achieved in gradient mode using water with 0.5% formic acid and acetonitrile with 0.5% formic acid and using a reverse phase C18 column. The electrospray ion source operated in negative and positive mode for the detection of glucosinolates and isothiocyanates, respectively, and the multiple reaction monitoring (MRM) was selected as acquisition mode. The method was validated following the ICH guidelines. Replicate experiments demonstrated a good accuracy (bias%<10%) and precision (CV%<10%). Detection limits and quantification limits are in the range of 1-400ng/mL for each analytes. Calibration curves were validated on concentration ranges from 0.05 to 50μg/mL. The method proved to be suitable for glucosinolates and isothiocyanates determination both in biomasses and in complex matrices such as food products enriched with glucosinolates, or nutraceutical bakery products. In addition, the developed method was applied to the simultaneous determination of glucosinolates and isothiocyanates in bakery product enriched with glucosinolates, to evaluate their thermal stability after different industrial processes from cultivation phases to consumer processing. PMID:26363943

For most normal-hearing listeners, absolute thresholds increase rapidly above about 16 kHz. One hypothesis is that the high-frequency limit of the hearing-threshold curve is imposed by the transmission characteristics of the middle ear, which attenuates the sound input [Masterton et al., J. Acoust. Soc. Am. 45, 966-985 (1969)]. An alternative hypothesis is that the high-frequency limit of hearing is imposed by the tonotopicity of the cochlea [Ruggero and Temchin, Proc. Nat. Acad. Sci. U.S.A. 99, 13206-13210 (2002)]. The aim of this study was to test these hypotheses. Forward-masked psychophysical tuning curves (PTCs) were derived for signal frequencies of 12-17.5 kHz. For the highest signal frequencies, the high-frequency slopes of some PTCs were steeper than the slope of the hearing-threshold curve. The results also show that the human auditory system displays frequency selectivity for characteristic frequencies (CFs) as high as 17 kHz, above the frequency at which absolute thresholds begin to increase rapidly. The findings suggest that, for CFs up to 17 kHz, the high-frequency limitation in humans is imposed in part by the middle-ear attenuation, and not by the tonotopicity of the cochlea.

The interaction between stream flow and bed forms creates an uneven distribution of near-bed energy heads, which is the driving force of hyporheic exchange. Owing to the large disparity of advection characteristic times in the stream and within the hyporheic zone, solute mass exchange is often modeled by considering the latter as an immobile region. In a recent contribution Gónzalez-Pinzón et al. (2013) showed that existing models employing this hypothesis are structurally inconsistent with the scaling revealed by the analysis of 384 breakthrough curves collected in 44 streams across five continents. Motivated by this result, we analyze the scaling characteristics of a model that we recently developed by combining the analytical solution of the advective flow within the hyporheic zone with a Lagrangian solute transport model. Results show that similarly to the experimental data our model predicts breakthrough curves with a constant skewness, irrespective of the stream size, and that the scaling of the first three moments observed by Gónzalez-Pinzón et al. (2013) is also respected. Moreover, we propose regression curves that relate the first three moments of the residence time distribution with the alternate bar dimensionless depth (YBM*), a quantity that is easily measurable in the field. The connection between BTC moments and YBM* opens new possibilities for modeling transport processes at the catchment scale.

The effect of the electrospraying of water in combination with a positive direct current (dc) streamer corona discharge generated in air was investigated in this paper. We employed high-speed camera visualizations and oscilloscopic discharge current measurements in combination with an intensified charge-coupled device camera for fast time-resolved imaging. The repetitive process of Taylor cone formation and droplet formation from the mass fragments of water during the electrospray was visualized. Depending on the applied voltage, the following intermittent modes of electrospraying typical for water were observed: dripping mode, spindle mode, and oscillating-spindle mode. The observed electrospraying modes were repetitive with a frequency of a few hundreds of Hz, as measured from the fast image sequences. This frequency agreed well with the frequency of the measured streamer current pulses. The presence of filamentary streamer discharges at relatively low voltages probably prevented the establishment of a continuous electrospray in the cone-jet mode. After each streamer, a positive glow corona discharge was established on the water filament tip, and it propagated from the stressed electrode along with the water filament elongation. The results show a reciprocal character of intermittent electrospraying of water, and the presence of corona discharge, where both the electrospray and the discharge affect each other. The generation of a corona discharge from the water cone depended on the repetitive process of the cone formation. Also, the propagation and curvature of the water filament were influenced by the discharge and its resultant space charge. Furthermore, these phenomena were partially influenced by the water conductivity.

Purpose The purpose of the present research was to develop a novel electrosprayed nanospherule providing the most optimized aqueous solubility and oral bioavailability for poorly water-soluble fenofibrate. Methods Numerous fenofibrate-loaded electrosprayed nanospherules were prepared with polyvinylpyrrolidone (PVP) and Labrafil® M 2125 as carriers using the electrospray technique, and the effect of the carriers on drug solubility and solvation was assessed. The solid state characterization of an optimized formulation was conducted by scanning electron microscopy, powder X-ray diffraction, differential scanning calorimetry, and Fourier transform infrared spectroscopic analyses. Oral bioavailability in rats was also evaluated for the formulation of an optimized nanospherule in comparison with free drug and a conventional fenofibrate-loaded solid dispersion. Results All of the electrosprayed nanospherule formulations had remarkably enhanced aqueous solubility and dissolution compared with free drug. Moreover, Labrafil M 2125, a surfactant, had a positive influence on the solubility and dissolution of the drug in the electrosprayed nanospherule. Increases were observed as the PVP/drug ratio increased to 4:1, but higher ratios gave no significant increases. In particular, an electrosprayed nanospherule composed of fenofibrate, PVP, and Labrafil M 2125 at the weight ratio of 1:4:0.5 resulted in a particle size of <200 nm with the drug present in the amorphous state. It demonstrated the highest solubility (32.51±2.41 μg/mL), an excellent dissolution (~85% in 10 minutes), and an oral bioavailability ~2.5-fold better than that of the free drug. It showed similar oral bioavailability compared to the conventional solid dispersion. Conclusion Electrosprayed nanospherules, which provide improved solubility and bioavailability, are promising drug delivery tools for oral administration of poorly water-soluble fenofibrate. PMID:26834471

Creating nanoparticles of beneficial nutraceuticals and pharmaceuticals has had a large surge of research due to the enhancement of absorption and bioavailability by decreasing their size. One of these ways is by electrohydrodynamic atomization, also known as electrospraying. In general, this novel process is done by forcing a liquid through a capillary nozzle and which is subjected to an electrical field. While there are different ways to create nanoparticles, the novel method of electrospraying can be beneficial over other types of nanoparticle formation. Reasons include high control over particle size and distribution by altering electrospray parameters (voltage, flow rate, distance, and time), higher encapsulation efficiency than other methods, and also it is a one step process without exposure to extreme conditions (Gomez-Estaca et. al. 2012, Jaworek and Sobcyzk 2008). The current study aimed to create a chitosan encapsulated theaflavin-2 enriched black tea extract (BTE) nanoparticles via electrospraying. The first step of this process was to create the smallest chitosan nanoparticles possible by altering the electrospray parameters and the chitosan-acetic acid solution parameters. The solution properties altered include chitosan molecular weight, acetic acid concentration, and chitosan concentration. Specifically, the electrospray parameters such as voltage, flow rate and distance from syringe to collector are the most important in determining particle size. After creating the smallest chitosan particles, the TF-2 enriched black tea extract was added to the chitosan-acetic acid solution to be electrosprayed. The particles were assessed with the following procedures: Atomic force microscopy (AFM) and scanning electron microscopy (SEM) for particle morphology and size, and loading efficiency with ultraviolet--visible spectrophotometer (UV-VIS). Chitosan-BTE nanoparticles were successfully created in a one step process. Diameter of the particles on average

Tool for use in electrical-discharge machining (EDM) guides EDM electrode in making curved holes. Guide rod fits in slot in arm, which moves through arc. Motion drives electrode into workpiece along desired curved path. Electrode burns into workpiece while arm rotates on spindle. Discharge cuts hole of same radius of curvature.

Structures capable of deployment into complex, three-dimensional trusses have well known space technology applications such as the support of spacecraft payloads, communications antennas, radar reflectors, and solar concentrators. Such deployable trusses could also be useful in terrestrial applications such as the rapid establishment of structures in military and emergency service situations, in particular with regard to the deployment of enclosures for habitat or storage. To minimize the time required to deploy such an enclosure, a single arch-shaped truss is preferable to multiple straight trusses arranged vertically and horizontally. To further minimize the time required to deploy such an enclosure, a synchronous deployment with a single degree of freedom is also preferable. One method of synchronizing deployment of a truss is the use of a series of gears; this makes the deployment sequence predictable and testable, allows the truss to have a minimal stowage volume, and the deployed structure exhibits the excellent stiffness-to-mass and strength-to-mass ratios characteristic of a truss. A concept for using gears with varying ratios to deploy a truss into a curved shape has been developed and appears to be compatible with both space technology applications as well as potential use in terrestrial applications such as enclosure deployment. As is the case with other deployable trusses, this truss is formed using rigid elements (e.g., composite tubes) along the edges, one set of diagonal elements composed of either cables or folding/hinged rigid members, and the other set of diagonal elements formed by a continuous cable that is tightened by a motor or hand crank in order to deploy the truss. Gears of varying ratios are used to constrain the deployment to a single degree of freedom, making the deployment synchronous, predictable, and repeatable. The relative sizes of the gears and the relative dimensions of the diagonal elements determine the deployed geometry (e

Surface topography of medical implants provides an important biophysical cue on guiding cellular functions at the cell-implant interface. However, few techniques are available to produce polymeric coatings with controlled microtopographies onto surgical implants, especially onto implant devices of small dimension and with complex structures such as drug-eluting stents. Therefore, the main objective of this study was to develop a new strategy to fabricate polymeric coatings using an electrospraying technique based on the uniqueness of this technique in that it can be used to produce a mist of charged droplets with a precise control of their shape and dimension. We hypothesized that this technique would allow facile manipulation of coating morphology by controlling the shape and dimension of electrosprayed droplets. More specifically, we employed the electrospraying technique to coat a layer of biodegradable polyurethane with tailored microtopographies onto commercial coronary stents. The topography of such stent coatings was modulated by controlling the ratio of round to stretched droplets or the ratio of round to crumped droplets under high electric field before deposition. The shape of electrosprayed droplets was governed by the stability of these charged droplets right after ejection or during their flight in the air. Using the electrospraying technique, we achieved conformal polymeric coatings with tailored microtopographies onto conductive surgical implants. The approach offers potential for controlling the surface topography of surgical implant devices to modulate their integration with surrounding tissues. PMID:26090663

Flexible transparent carbon nanotube (CNT) electrodes were fabricated by electrospray deposition, a large-area scalable and cost-effective process. The carbon nanotubes were dispersed in N,N-dimethylformamide (DMF) and deposited on polyethylene terephthalate (PET) substrates by electrospray deposition process at room temperature and atmospheric pressure. Major process variables were characterized and optimized for the electrospray process development such as electric field between nozzle and substrates, CNT solution flowrate, gap between nozzle and substrates, solution concentration, solvent properties and surface temperature. The sheet resistance of the electrospray deposited CNT films were reduced by HNO3 doping process. 169 Omega/sq sheet resistance and 86% optical transmittance was achieved with low surface roughness of 1.2 nm. The films showed high flexibility and transparency, making them potential replacements of ITO or ZnO in such as solid state lighting, touch panels, and solar cells. Electrospray process is a scalable process and we believe that this process can be applied for large area carbon nanotube film formation. PMID:24205613

Microsphere-based controlled release technologies have been utilized for the long-term delivery of proteins, peptides and antibiotics, although their synthesis poses substantial challenges owing to formulation complexities, lack of scalability, and cost. To address these shortcomings, we used the electrospray process as a reproducible, synthesis technique to manufacture highly porous (>94%) microspheres while maintaining control over particle structure and size. Here we report a successful formulation recipe used to generate spherical poly(lactic-co-glycolic) acid (PLGA) microspheres using the electrospray (ES) coupled with a novel thermally induced phase separation (TIPS) process with a tailored Liquid Nitrogen (LN2) collection scheme. We show how size, shape and porosity of resulting microspheres can be controlled by judiciously varying electrospray processing parameters and we demonstrate examples in which the particle size (and porosity) affect release kinetics. The effect of electrospray treatment on the particles and their physicochemical properties are characterized by scanning electron microscopy, confocal Raman microscopy, thermogravimetric analysis and mercury intrusion porosimetry. The microspheres manufactured here have successfully demonstrated long-term delivery (i.e. 1week) of an active agent, enabling sustained release of a dye with minimal physical degradation and have verified the potential of scalable electrospray technologies for an innovative TIPS-based microsphere production protocol. PMID:26803601

Despite widespread interest in applying lab-on-a-chip technologies to mass spectrometry (MS)-based analyses, the coupling of microfluidics to electrospray ionization (ESI)-MS remains challenging. We report a robust, integrated poly(dimethylsiloxane) microchip interface for ESI-MS using simple and widely accessible microfabrication procedures. The interface uses an auxiliary channel to provide electrical contact in the Taylor cone of the electrospray without sample loss or dilution. The electric field at the channel terminus is enhanced by two vertical cuts that cause the interface to taper to a line rather than to a point, and the formation of small Taylor cones at the channel exit ensures sub-nL post-column dead volumes. While comparable ESI-MS sensitivities were achieved using both microchip and conventional fused silica capillary emitters, stable cone-jet mode electrospray could be established over a far broader range of flow rates (from 50–1000 nL/min) and applied potentials using the microchip emitters. This special feature of the microchip emitter should minimize the fine tuning required for electrospray optimization and make the stable electrospray more resistant to external perturbations.

The fabrication of tailored microparticles for delivery of therapeutics is a challenge relying upon a complex interplay between processing parameters and materials properties. The emerging use of electrospraying allows better tailoring of particle morphologies and sizes than current techniques, critical to reproducible release profiles. While dry encapsulation of proteins is essential for the release of active therapeutics from microparticles, it is currently uncharacterized in electrospraying. To this end, poly(ethylene glycol) (PEG) was assessed as a micronizing and solubilizing agent for dry protein encapsulation and release from electrosprayed particles made from polycaprolactone (PCL). The physical effect of PEG in protein-loaded poly(lactic-co-glycolic acid) (PLGA) particles was also studied, for comparison. The addition of 5-15 wt% PEG 6 kDa or 35 kDa resulted in reduced PCL particle sizes and broadened distributions, which could be improved by tailoring the electrospraying processing parameters, namely by reducing polymer concentration and increasing flow rate. Upon micronization, protein particle size was reduced to the micrometer domain, resulting in homogenous encapsulation in electrosprayed PCL microparticles. Microparticle size distributions were shown to be the most determinant factor for protein release by diffusion and allowed specific control of release patterns. PMID:24657821

Surface topography of medical implants provides an important biophysical cue on guiding cellular functions at the cell-implant interface. However, few techniques are available to produce polymeric coatings with controlled microtopographies onto surgical implants, especially onto implant devices of small dimension and with complex structures such as drug-eluting stents. Therefore, the main objective of this study was to develop a new strategy to fabricate polymeric coatings using an electrospraying technique based on the uniqueness of this technique in that it can be used to produce a mist of charged droplets with a precise control of their shape and dimension. We hypothesized that this technique would allow facile manipulation of coating morphology by controlling the shape and dimension of electrosprayed droplets. More specifically, we employed the electrospraying technique to coat a layer of biodegradable polyurethane with tailored microtopographies onto commercial coronary stents. The topography of such stent coatings was modulated by controlling the ratio of round to stretched droplets or the ratio of round to crumped droplets under high electric field before deposition. The shape of electrosprayed droplets was governed by the stability of these charged droplets right after ejection or during their flight in the air. Using the electrospraying technique, we achieved conformal polymeric coatings with tailored microtopographies onto conductive surgical implants. The approach offers potential for controlling the surface topography of surgical implant devices to modulate their integration with surrounding tissues. PMID:26090663

Elucidating reaction mechanisms is important for advancing many areas of science such as catalyst development. It is often difficult to probe fast reactions at ambient conditions with high temporal resolution. In addition, systems involving reagents that cross-react require analytical methods that can minimize interaction time and specify their order of introduction into the reacting system. Here, we explore the utility of transmission mode desorption electrospray ionization (TM-DESI) for reaction monitoring by directing a microdroplet spray towards a series of meshes with micrometer-sized openings coated with reagents, an approach we call multistage reactive TM-DESI (TM (n) -DESI, where n refers to the number of meshes; n = 2 in this report). Various stages of the reaction are initiated at each mesh surface, generating intermediates and products in microdroplet reaction vessels traveling towards the mass spectrometer. Using this method, we investigated the reactivity of iron porphyrin catalytic hydroxylation of propranolol and other substrates. Our experimental results indicate that TM (n) -DESI provides the ability to spatially separate reagents and control their order of introduction into the reacting system, thereby minimizing unwanted reactions that lead to catalyst deactivation and degradation products. In addition, comparison with DESI-MS analyses (the Zare and Latour laboratories published results suggesting accessible reaction times <1 ms) of the reduction of dichlorophenolindophenol by L-ascorbic acid suggest that TM (1) -DESI can access reaction times less than 1 ms. Multiple meshes allow sequential stages of desorption/ionization per MS scan, increasing the number of analytes and reactions that can be characterized in a single experiment. PMID:26091888

An electrospray ionization (ESI) source was designed, fabricated and then installed on a VG TRIO-2 quadrupole mass spectrometer. A gold coated 50-[mu]m fused silica capillary was used instead of the conventional stainless steel needle. Analytes are desorbed into the gas phase via a heated metal transport capillary and are focused through a set of five electrostatic lenses into the analyzer region of the mass spectrometer. Environmentally significant compounds such as pesticides and herbicides that are polar, nonvolatile and thermally labile are not readily analyzed by conventional gas chromatography/mass spectrometry (GC/MS). Thirty pesticides from the 13 classes of carbamate, organophosphorus, organochlorine, bipyridyl, phthalimide, urea, carboxyllic acid, hydroxycoumarin, triazine, indandione, dinitroaniline, pyrethrin, and thiocarbamate were analyzed using this method. Analysis of these samples showed that addition of acid to the neat sample did not appreciably increase the protonated analyte signal nor the total ion current for any of the samples analyzed. This observation together with the extremely low pKa values of these pesticides, calculated by SPARC, indicates that the protonated analytes are formed in the gas rather than in the condensed phase. Sodium and ammonium ions were added to these pesticides but in no case was the total ion current increased over that from the neat sample. Solvent studies showed that 50/50 mixtures of methanol/water and acetonitrile/water are both suitable solvent systems but that a methanol fraction of 30% appears to be ideal for some of the pesticides studied. Evidence of radical cation formation was observed when pure acetonitrile was used. It was demonstrated, by spiking 5 carbamate pesticides into Yellowstone River water, that ESI/MS by the direct injection method is a potential candidate as a rapid screening method for pesticides in natural waters.

Time resolved measurements show that during a desorption electrospray ionization (DESI) experiment, the current initially rises sharply, followed by an exponential decrease to a relatively steady current. When the high voltage on the spray emitter is switched off, the current drops to negative values, suggesting that the direction of current flow in the equivalent DESI circuit is reversed. These data demonstrate that the DESI source behaves as a dc capacitor and that the addition of a surface between the sprayer and the counter electrode in DESI introduces a new electrically active element into the system. The charging and discharging behavior was observed using different surfaces and it could be seen both by making current measurements on a plate at the entrance to the mass spectrometer as well as by measuring ion current in the linear ion trap within the vacuum system of the mass spectrometer. The magnitude of the steady state current obtained without analyte present on the surface is different for different surface materials, and different capacitor time constants of the equivalent RC circuits were calculated for different DESI surfaces. The PTFE surface has by far the greatest time constant and is also able to produce the highest DESI currents. Surface properties play a crucial role in charge transfer during DESI in addition to the effects of the chemical properties of the analyte. It is suggested that surface energy (wettability) is an important factor controlling droplet behavior on the surface. The experimental data are correlated with critical surface tension values of different materials. It is proposed, based on the results presented, that super-hydrophobic materials with extremely high contact angles have the potential to be excellent DESI substrates. It is also demonstrated, using the example of the neurotransmitter dopamine, that the surface charge that develops during a DESI-MS experiment can cause electrochemical oxidation of the analyte. PMID

We have used an infrared laser to ablate materials under ambient conditions that were captured in solvent droplets. The droplets were either deposited on a MALDI target for off-line analysis by MALDI time-of-flight mass spectrometry or flow-injected into a nanoelectrospray source of an ion trap mass spectrometer. An infrared optical parametric oscillator (OPO) laser system at 2.94 μm wavelength and approximately 1 mJ pulse energy was focused onto samples for ablation at atmospheric pressure. The ablated material was captured in a solvent droplet 1-2 mm in diameter that was suspended from a silica capillary a few millimeters above the sample target. Once the sample was transferred to the droplet by ablation, the droplet was deposited on a MALDI target. A saturated matrix solution was added to the deposited sample, or in some cases, the suspended capture droplet contained the matrix. Peptide and protein standards were used to assess the effects of the number of IR laser ablation shots, sample to droplet distance, capture droplet size, droplet solvent, and laser pulse energy. Droplet collected samples were also injected into a nanoelectrospray source of an ion trap mass spectrometer with a 500 nL injection loop. It is estimated that pmol quantities of material were transferred to the droplet with an efficiency of approximately 1%. The direct analysis of biological fluids for off-line MALDI and electrospray was demonstrated with blood, milk, and egg. The implications of this IR ablation sample transfer approach for ambient imaging are discussed.

The microchannel array plate (MCP) is a photoelectric detector with an imaging capability comparable to that of a photographic plate. Recently MCPs in which the channels are curved to inhibit ion feedback have become available. These devices represent a major advance in MCP technology, since a single curved-channel MCP can be operated stably at high gain in the pulse-counting mode without any of the problems of stability of response or short lifetime reported for 'chevron' MCP detectors. Attention is given to the mode of operation of channel electron multipliers (CEM) and MCP, curved-channel MCP, test procedures, and performance characteristics. The accumulated test data show that the fundamental operating characteristics of the curved-channel MCP are directly related to those for the CEM.

We investigate Poiseuille channel flow through intrinsically curved media, equipped with localized metric perturbations. To this end, we study the flux of a fluid driven through the curved channel in dependence of the spatial deformation, characterized by the parameters of the metric perturbations (amplitude, range, and density). We find that the flux depends only on a specific combination of parameters, which we identify as the average metric perturbation, and derive a universal flux law for the Poiseuille flow. For the purpose of this study, we have improved and validated our recently developed lattice Boltzmann model in curved space by considerably reducing discrete lattice effects.

We investigate Poiseuille channel flow through intrinsically curved media, equipped with localized metric perturbations. To this end, we study the flux of a fluid driven through the curved channel in dependence of the spatial deformation, characterized by the parameters of the metric perturbations (amplitude, range, and density). We find that the flux depends only on a specific combination of parameters, which we identify as the average metric perturbation, and derive a universal flux law for the Poiseuille flow. For the purpose of this study, we have improved and validated our recently developed lattice Boltzmann model in curved space by considerably reducing discrete lattice effects. PMID:27176437

Hollow fibre liquid-phase microextraction (LPME) and desorption electrospray ionization mass spectrometry (DESI-MS) were evaluated for the identification and quantification of basic drugs in human urine samples. The selective extraction capabilities of three-phase LPME provided a significant reduction in the matrix effects otherwise observed in direct DESI-MS analysis of urine samples. Aqueous LPME extracts (in 10 mM HCl) were deposited on porous Teflon, dried at room temperature, and the dried spots were then analyzed directly with DESI-MS in full scan mode. Pethidine, diphenhydramine, nortriptyline, and methadone were used as model compounds for identification, and their limits of identification were determined to be 100, 25, 100, and 30 ng/mL, respectively. In a reliability test with 19 spiked urine samples, 100% of the positive samples containing the model drugs in concentrations at or above the limit of identification were identified. Diphenhydramine was used as a model compound for quantitative analysis with diphenhydramine-d(5) as an internal standard. The calibration curve was linear in the range 50-2000 ng/mL (R(2) = 0.992) with a limit of quantification at approximately 140 ng/mL. The intra- and inter-day relative standard deviations were <9.5%. In a reliability test with six spiked urine samples, deviations between the measured and the true values for diphenhydramine were in the range 0.2-22.9%. PMID:22173801

A 2-cm cartridge has been used for separation before electrospray mass spectrometric analysis of pharmaceutical compounds in cell culture media, alleviating the need for sample extraction and desalting procedures. Nine representative pharmaceuticals listed in the biopharmaceutical classification system (BCS) were chosen as the candidate compounds and Hank's balanced salt solution with Hepes buffer (HBSS-Hepes buffer) was used as the cell-culture medium in an effort to study permeability of chemicals through cell monolayers. Effects of several conditions, e.g. pH and buffer concentration in the mobile phase, flow rate, and temperature on separation efficiency were examined. The nine pharmaceuticals were separated within 2 min by use of a 2-cm C(8) cartridge. Relative standard deviations (RSD) from repeated analysis within the same day or over five days were 0.03-0.2% for retention times and 0.6-5.3% for peak areas; antipyrine was used as internal standard. Calibration curves based on peak-area measurements were linear over the range 0.1-20 micro mol L(-1). The HBSS-Hepes buffer did not interfere with separation and detection; identical separation and peak intensity were obtained when the samples were separately prepared in distilled water or in the culture medium. PMID:12207243

Development of a rapid, sensitive and selective method for the determination of antimigraine drugs from human serum is essential for understanding the pharmacokinetics of these drugs when administered concurrently. Solid phase extraction (SPE) using Oasis HLB was used to extract the drugs (sumatriptan, naratriptan, zolmitriptan and rizatriptan) and the internal standard bufotenine from serum. A method based on liquid chromatography/tandem mass spectrometry (LC/MS/MS) was developed and validated to simultaneously quantitate these antimigraine drugs from human serum. The precursor and major product ions of the analytes were monitored on a triple quadrupole mass spectrometer with positive ion electrospray ionization (ESI) in the multiple reaction monitoring (MRM) mode. The base peak in all the analytes is formed by alpha cleavage associated with protonation of the secondary amine. Mechanisms for the formation of the collision-induced dissociation products of these antimigraine compounds are proposed. Linear calibration curves were generated from 1-100 ng/mL with all coefficients of determination greater than 0.99. The inter- and intraday precision (%RSD) were less than 9.3% and accuracy (%error) was less than 9.8% for all components. The limits of detection (LOD) for the method were 250 pg/mL for sumatriptan and 100 pg/mL for the remaining analytes based on a signal-to-noise ratio of 3. PMID:10637423

A new sensitive method for the simultaneous determination of 12 trichothecenes (deoxynivalenol, nivalenol, 3-acetyldeoxynivalenol, 15-acetyldeoxynivalenol, fusarenon X, T-2 toxin, HT-2 toxin, neosolaniol, monoacetoxyscirpenol, diacetoxyscirpenol, T-2 triol, and T-2 tetraol) by liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) is presented. The development of the method and investigations on the matrix influence on the MS signal are described in particular. The matrix effect was thereby minimized by using an internal standard, a special mobile phase, and specific fragmentation parameters. The sample was extracted with acetonitrile/water (84:16, v/v), and the extract was cleaned up with a MycoSep 227 column. Quantification was based on the internal standard de-epoxy-deoxynivalenol. Calibration curves were linear between 16 and 1600 ng/g, and the limits of detection ranged from 0.18 to 5.0 ng/g. The developed method was applied for the determination of trichothecenes in 120 naturally contaminated wheat and oat samples. PMID:16277381

Ambient ionization (AI) techniques have been widely used in chemistry, medicine, material science, environmental science, forensic science. AI takes advantage of direct desorption/ionization of chemicals in raw samples under ambient environmental conditions with minimal or no sample preparation. However, its quantitative accuracy is restricted by matrix effects during the ionization process. To improve the quantitative accuracy of AI, a matrix reference material, which is a particular form of measurement standard, was coupled to an AI technique in this study. Consequently the analyte concentration in a complex matrix can be easily quantified with high accuracy. As a demonstration, this novel method was applied for the accurate quantification of creatinine in serum by using extractive electrospray ionization (EESI) mass spectrometry. Over the concentration range investigated (0.166 ~ 1.617 μg/mL), a calibration curve was obtained with a satisfactory linearity (R2 = 0.994), and acceptable relative standard deviations (RSD) of 4.6 ~ 8.0% (n = 6). Finally, the creatinine concentration value of a serum sample was determined to be 36.18 ± 1.08 μg/mL, which is in excellent agreement with the certified value of 35.16 ± 0.39 μg/mL. PMID:26759071

We describe a simple stable isotope dilution method for accurate and precise measurement of γ-aminobutyric acid (GABA), a major inhibitory neurotransmitter in human cerebrospinal fluid (CSF) as a clinical diagnostic test. Determination of GABA in CSF (50 μL) was performed utilizing high performance liquid chromatography coupled with electrospray positive ionization tandem mass spectrometry (HPLC-ESI-MS/MS). Analysis of free and total GABA requires two individual sample preparations and mass spectrometry analyses. Free GABA in CSF is determined by a 1:2 dilution with internal standard (GABA-D2) and injected directly onto the HPLC-ESI-MS/MS system. Determination of total GABA in CSF requires additional sample preparation in order to hydrolyze all the bound GABA in the sample to the free form. This requires hydrolyzing the sample by boiling in acidic conditions (hydrochloric acid) for 4 h. The sample is then further diluted 1:10 with a 90 % acetonitrile/0.1 % formic acid solution and injected into the HPLC-ESI-MS/MS system. Each assay is quantified using a five-point standard curve and is linear from 6 nM to 1000 nM and 0.63 μM to 80 μM for free and total GABA, respectively. PMID:26602123

A method using liquid chromatography electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) for the determination of trace levels of five macrolide antibiotics (spiramycin, tilmicosin, oleandomycin, erythromycin, and tylosin) in eggs is presented. Data acquisition under MS/MS was achieved by applying multiple reaction monitoring (MRM) of two or three fragment ion transitions to provide a high degree of sensitivity and specificity for both quantification and confirmation. Matrix-matched standard calibration curves were used to achieve the best accuracy of the method. A fully nested experimental design was used to study the measurement uncertainty arising from intermediate precision and trueness or proportional bias. The overall recoveries, that is, those determined by the nested experiments, of spiramycin, tilmicosin, oleandomycin, erythromycin, and tylosin at fortified levels of 60, 100, 200, and 300 microg/kg were 96.8, 98.2, 98.3, 98.8, and 95.4%, respectively. The LC/ESI-MS/MS method detection limits (S/N > or = 3:1) of five macrolides were <1.0 microg/kg. PMID:15769104

A confirmatory method using liquid chromatography-electrospray ionization tandem mass spectrometry for determination of five macrolide antibiotics including spiramycin, tilmicosin, oleandomycin, erythromycin, and tylosin in raw milk is presented. Macrolides were extracted from raw milk by acetonitrile, and sample extracts were further cleaned up using solid-phase extraction cartridges. Data acquisition was achieved using multiple reaction monitoring, that is, two transitions, to provide a high degree of sensitivity and specificity. Matrix-matched standard calibration curves with the use of roxithromycin as an internal standard were utilized to achieve the best accuracy of the method. Both a conventional validation procedure and a designed experiment were applied to study the accuracy and precision of the method. The measurement uncertainty arising from accuracy and precision was estimated. The method accuracy, expressed as a percentage of overall recovery, was approximately 100%, and its intermediate precision was <10%. LC-ESI/MS/MS method detection limits (S/N > or = 3:1) of five macrolides were <0.3 microg/kg. PMID:16608203

Docetaxel is a second-generation taxane and is used clinically as an anti-neoplastic agent in cancer chemotherapy via an anti-mitotic mechanism. Its efficacy is limited to a narrow therapeutic window. Inappropriately high concentrations may cause erythema, fluid retention, nausea, diarrhea, and neutropenia. As a result, dosing recommendations have changed from high dosage loading every 3 weeks to lower dosage loading weekly. We describe a method that can be used for therapeutic drug monitoring of docetaxel levels using turbulent flow liquid chromatography electrospray tandem mass spectrometry (TFC-HPLC-ESI-MS/MS). The method is rapid, requiring only 6.3 min per analytical run following a simple protein crash. The method requires only 100 μL of serum. Concentrations of docetaxel were quantified by a calibration curve relating the peak-area ratio of docetaxel to a deuterated internal standard (docetaxel-D9). The method was linear from 7.8 to 1000 ng/mL, with imprecision ≤6.2 %. PMID:26660181

A sensitive and specific method using a one-step liquid-liquid extraction (LLE) with ethyl acetate followed by high-performance liquid chromatography (HPLC) coupled with positive ion electrospray ionization tandem mass spectrometry (ESI-MS/MS) detection was developed and validated for the determination of roxatidine in human plasma using famotidine as an internal standard (IS). Data acquisition was carried out in multiple reaction monitoring (MRM) mode, by monitoring the transitions m/z 307.3-->107.1 for roxatidine and m/z 338.4-->189.1 for famotidine. Chromatographic separation was performed on a reverse phase Hydrosphere C(18) column at 0.2 mL min(-1) using a mixture of methanol-ammonium formate buffer as mobile phase (20:80, v/v; adjusted to pH 3.9 with formic acid). The achieved lower limit of quantification (LLOQ) was 1.0 ng mL(-1) and the standard calibration curve for roxatidine was linear (r(2)=0.998) over the studied range (1-1000 ng mL(-1)) with acceptable accuracy and precision. Roxatidine was found to be stable in human plasma samples under short-, long-term storage and processing conditions. The developed method was validated and successfully applied to the bioequivalence study of roxatidine administrated as a single oral dose (75 mg as roxatidine acetate hydrochloride) to healthy female Korean volunteers. PMID:18977187

Organophosphate nerve agents (OPNAs) are some of the most widely used and proliferated chemical warfare agents. As evidenced by recent events in Syria, these compounds remain a serious military and terrorist threat to human health because of their toxicity and the ease with which they can be used, produced and stored. There are over 2,000 known, scheduled compounds derived from common parent structures with many more possible. To address medical, forensic, attribution, remediation and other requirements, laboratory systems have been established to provide the capability to analyze 'unknown' samples for the presence of these compounds. Liquid chromatography/mass spectrometric methods have been validated and are routinely used in the analysis of samples for a very limited number of these compounds, but limited data exist characterizing the electrospray ionization (ESI) and mass spectrometric fragmentation pathways of the compound families. This report describes results from direct infusion ESI/MS, ESI/MS(2) and ESI/MS(3) analysis of 14 G and V agents, the major OPNA families, using an AB Sciex 4000 QTrap. Using a range of conditions, spectra were acquired and characteristic fragments identified. The results demonstrated that the reproducible and predictable fragmentation of these compounds by ESI/MS, ESI/MS(2) and ESI/MS(3) can be used to describe systematic fragmentation pathways specific to compound structural class. These fragmentation pathways, in turn, may be useful as a predictive tool in the analysis of samples by screening and confirmatory laboratories to identify related compounds for which authentic standards are not readily available. PMID:25519457

Electrochemistry (EC) combined with mass spectrometry (MS) is a powerful tool for elucidation of electrochemical reaction mechanisms. However, direct online analysis of electrochemical reaction in aqueous phase was rarely explored. This paper presents the online investigation of several electrochemical reactions with biological relevance in the aqueous phase, such as nitrosothiol reduction, carbohydrate oxidation, and carbamazepine oxidation using desorption electrospray ionization mass spectrometry (DESI-MS). It was found that electroreduction of nitrosothiols [e.g., nitrosylated insulin B (13-23)] leads to free thiols by loss of NO, as confirmed by online MS analysis for the first time. The characteristic mass shift of 29 Da and the reduced intensity provide a quick way to identify nitrosylated species. Equally importantly, upon collision-induced dissociation (CID), the reduced peptide ion produces more fragment ions than its nitrosylated precursor ion (presumably the backbone fragmentation cannot compete with the facile NO loss for the precursor ion), thus facilitating peptide sequencing. In the case of saccharide oxidation, it was found that glucose undergoes electro-oxidation to produce gluconic acid at alkaline pH, but not at neutral and acidic pHs. Such a pH-dependent electrochemical behavior was also observed for disaccharides such as maltose and cellobiose. Upon electrochemical oxidation, carbamazepine was found to undergo ring contraction and amide bond cleavage, which parallels the oxidative metabolism observed for this drug in leucocytes. The mechanistic information of these redox reactions revealed by EC/DESI-MS would be of value in nitroso-proteome research and carbohydrate/drug metabolic studies. PMID:26242804

Electrochemistry (EC) combined with mass spectrometry (MS) is a powerful tool for elucidation of electrochemical reaction mechanisms. However, direct online analysis of electrochemical reaction in aqueous phase was rarely explored. This paper presents the online investigation of several electrochemical reactions with biological relevance in the aqueous phase, such as nitrosothiol reduction, carbohydrate oxidation, and carbamazepine oxidation using desorption electrospray ionization mass spectrometry (DESI-MS). It was found that electroreduction of nitrosothiols [e.g., nitrosylated insulin B (13-23)] leads to free thiols by loss of NO, as confirmed by online MS analysis for the first time. The characteristic mass shift of 29 Da and the reduced intensity provide a quick way to identify nitrosylated species. Equally importantly, upon collision-induced dissociation (CID), the reduced peptide ion produces more fragment ions than its nitrosylated precursor ion (presumably the backbone fragmentation cannot compete with the facile NO loss for the precursor ion), thus facilitating peptide sequencing. In the case of saccharide oxidation, it was found that glucose undergoes electro-oxidation to produce gluconic acid at alkaline pH, but not at neutral and acidic pHs. Such a pH-dependent electrochemical behavior was also observed for disaccharides such as maltose and cellobiose. Upon electrochemical oxidation, carbamazepine was found to undergo ring contraction and amide bond cleavage, which parallels the oxidative metabolism observed for this drug in leucocytes. The mechanistic information of these redox reactions revealed by EC/DESI-MS would be of value in nitroso-proteome research and carbohydrate/drug metabolic studies.

A finite-element Galerkin formulation has been developed to study transverse magnetic (TM) wave propagation in 2-D S-curved ducts with both perfectly conducting and absorbing walls. The reflection and transmission at the entrances and the exits of the curved ducts are determined by coupling the finite-element solutions in the curved ducts to the eigenfunctions of an infinite, uniform, perfectly conducting duct. Example solutions are presented for a double mitred and S-ducts of various lengths. The length of the S-duct is found to significantly effect the reflective characteristics of the duct. Also, the effect of curvature on an absorbing duct is illustrated.

Full-dimensional computational fluid dynamics (CFD) simulations are presented for nano electrospray ionization (ESI) with various emitter designs. Our CFD electrohydrodynamic simulations are based on the Taylor-Melcher leaky-dielectric model, and the volume of fluid technique for tracking the fast-changing liquid-gas interface. The numerical method is first validated for a conventional 20 μm inner diameter capillary emitter. The impact of ESI voltage, flow rate, emitter tapering, surface hydrophobicity, and fluid conductivity on the nano-ESI behavior are thoroughly investigated and compared with experiments. Multi-electrospray is further simulated with 2-hole and 3-hole emitters with the latter having a linear or triangular hole arrangement. The simulations predict multi-electrospray behavior in good agreement with laboratory observations. PMID:22706328

On-line micellar electrokinetic chromatography (MEKC)-electrospray ionization mass spectrometry (ESIMS) is demonstrated for the analysis of chlorotriazine herbicides and barbiturates. In this study, the micellar velocity is directly manipulated by the adjustment of electroosmosis rather than the electrophoretic velocity of the micelle. The electroosmotic flow is adjusted against the electrophoretic velocity of the micelle by changing the solution pH in MEKC. The elimination of MEKC surfactant introduction into ESIMS is achieved with an anodically migrating micelle, moving away from the electrospray interface. The effects of moving surfactant boundary in the MEKC capillary on separation efficiency and resolution of triazine herbicides and barbiturates are investigated. The mass detection of herbicides and barbiturates sequentially eluted from the MEKC capillary is acquired using the positive and negative electrospray modes, respectively. 30 refs., 8 figs., 3 tabs.

Solvent dyes are used to color refined petroleum products to enable differentiation between gasoline, diesel, and jet fuels. Analysis for these dyes in the hydrocarbon product is difficult due to their very low concentrations in such a complex matrix. Flow injection analysis/electrospray ionization/mass spectrometry in both negative and positive mode was used to optimize ionization of ten typical solvent dyes. Samples of hydrocarbon product were analyzed under similar conditions. Positive electrospray ionization produced very complex spectra, which were not suitably specific for targeting only the dyes. Negative electrospray ionization produced simple spectra because aliphatic and aromatic moieties were not ionized. This enabled screening for a target dye in samples of hydrocarbon product from a spill.

This electrospray technology works by applying the desired chemicals onto a substrate as electrically generated, charged sprays. By imposing a potential difference between the application nozzle and the target, it is possible to precisely direct and control the spray. This electrospray method of application gives a small droplet size and a relatively uniform size distribution, with the added advantage of an easily controllable spray angle. It potentially offers substantial improvement over traditional methods in the area of application uniformity, resulting in improved product quality. Additionally, since the chemicals are electrically directed straight onto the fiber with a minimum of overspray, the electrospray method holds promise in the area of waste reduction, resulting in lowered production cost.

Titanium dioxide thin film plays an important role in thin film solar cells, and has promising future in everyday applications including air cleaning and self-cleaning glass. With the concepts of flexible solar cells and wearable devices being more and more popular, there is increasing interest to coat titanium dioxide thin films on flexible substrates, such as aluminum foils. Many methods have been used to fabricate titanium dioxide thin films, such as dip-coating, spin coating, aerosol spray, plasma-assisted coating, electrospraying, and so on. Among them, electrospraying is especially suitable for thin film deposition on flexible substrates. This work reports fabrication of dense and uniform titanium dioxide thin films on glass as well as flexible aluminum foil using multi-jet electrospraying technique.

To interpolate a sequence of points in Euclidean space, parabolic splines can be used. These are curves which are piecewise quadratic. To interpolate between points in a (semi-)Riemannian manifold, we could look for curves such that the second covariant derivative of the velocity is zero. We call such curves Jupp and Kent quadratics or JK-quadratics because they are a special case of the cubic curves advocated by Jupp and Kent. When the manifold is a Lie group with bi-invariant metric, we can relate JK-quadratics to null Lie quadratics which arise from another interpolation problem. We solve JK-quadratics in the Lie groups SO(3) and SO(1,2) and in the sphere and hyperbolic plane, by relating them to the differential equation for a quantum harmonic oscillator00.

The present work studies the mechanics of turbulent drag reduction over curved surfaces by riblets. The effects of surface modification on flow separation over steep and smooth curved surfaces are investigated. Four types of two-dimensional surfaces are studied based on the morphometric parameters that describe the body of a blue whale. Local measurements of mean velocity and turbulence profiles are obtained through laser Doppler anemometry (LDA) and particle image velocimetry (PIV).

Nalmefene is an opioid antagonist used in the treatment of alcoholism and opioid overdose. A highly sensitive method was developed to measure nalmefene in human and rabbit plasma and rabbit serum. Nalbuphine was used as internal standard. Liquid-liquid extraction was applied using n-butyl chloride/acetonitrile (4:1). High-performance liquid chromatography interfaced by electrospray ionization to a tandem mass spectrometer was used for quantitation. Primary validation experiments were conducted using human plasma then it was cross-validated in rabbit plasma and rabbit serum. Specificity (peak-area ratio of blank plasma or serum to its internal standard as percent of peak-area ratio of blank plasma or serum fortified with 0.1 ng/mL nalmefene to its internal standard) ranged from 2.09 to 5.29 with a mean of 3.21% for human plasma and from 4.08 to 6.63 with a mean of 5.55% for rabbit plasma and from 2.47 to 6.17 with a mean of 3.62% for rabbit serum. The mean recovery for nalmefene was 80% in human plasma. The calibration range was from 0.1 to 100 ng/mL. Intrarun accuracy of the lower limit of quantitation (0.1 ng/mL) in all matrices was within 18.0% of target with intrarun precision within 13.6%. At 0.3, 35, and 75 ng/mL, the intrarun accuracy in all matrices was within 11.9% of target with intrarun precision within 6.6%. The inter-run accuracy in human plasma was within 8.0% of target with inter-run precision within 6.6%. Nalmefene was stable in human and rabbit plasma and rabbit serum for up to 24 h at room temperature and in human plasma after three freeze-thaw cycles. Following intravenous injection of 5 mg/kg nalmefene to rabbits, the mean area under curve for 0 to 24 h was 1116 (ng)(mL)(-1)(h), and the mean plasma clearance was 67.9 (mL)(min)(-1)(kg)(-1). PMID:15842759

An application of electrospray ionization/mass spectrometry for identification of various commercially refined fuels using the unique signature of polar components, was investigated. The samples were analyzed by mass spectrometry using negative electrospray on an Agilent Series 1100 liquid chromatograph/mass spectrometer. These analysis were applied to hydrocarbon samples from a large, long-term fuel spill which were taken from the subsurface and different extent of biodegradation or weathering. The technique provided rapid identification of hydrocarbons released into the environment because these polar compounds are unique in different fuels.

Current electrospray ion trap methodology for rapid mixture analysis of proteins used for the identification of microorganisms is described. Development of ion/ion reaction techniques (e.g. reactions of multiply-charged protein cations with singly-charged anions) from both a fundamental and practical approach are presented, detailing the necessary steps and considerations involved in complex mixture analysis. Data describing the reduction of the initial charge states of electrospray ions to arbitrarily low values, the utility of ion/ion reactions for mixture separation on the millisecond time scale, and effects of excess singly-charged reactants on detection and storage efficiency are illustrated.

We describe recent work in which we revisit the database of historical X-Ray nova (XRN) light curves compiled by Chen, Shrader & Livio (1997, ApJ 491, 312), augmented by subsequent events recorded by RXTE, in an attempt to gain a better understanding of the outburst phenomenon. Previously, we demonstrated that, given the occurrence of an instability in the mass transfer rate from the secondary, a model based on viscous diffusion of matter through the disk (Wood et al, 2001, astro-ph/0108189) we could reproduce a large number of fast-rise exponential decay (FRED) type XRN light curves. We augment this effort by considering deviations from the FRED form, such as plateaus and power-law decay forms are also considered within this framework. More complex structures are, in a number of instances, successfully modeled as a superposition of mass- injection, diffusive propagation events. In addition, for a large number of cases, we perform a joint analysis of optical light curve data. In particular, we will attempt to characterize empirical characteristics such as possible tie lags, and relative decay time scales, and then interpret such effects withing the context of diffusive propagation in the disk.

We describe surface enhanced Raman spectroscopy (SERS) experiments in which molecular coverage is systematically varied from 3.8 x 105 to 3.8 x 102 to 0.38 molecules/μm2 using electrospray deposition of ethanolic 4,4’-dimercaptostilbene (DMS) solutions. The plasmonic SERS substrate used herein consists of a well-characterized 2-dimensional (2D) array of silver nanospheres [see El-Khoury et al., J. Chem. Phys., 2014, 141, 214308], previously shown to feature uniform topography and plasmonic response, as well as intense SERS activity. When compared to their ensemble averaged analogues, the spatially and temporally averaged spectra of a single molecule exhibit several unique features including: (i) distinct relative intensities of the observable Raman-active vibrational states, (ii) more pronounced SERS backgrounds, and (iii) broader Raman lines indicative of faster vibrational dephasing. The first observation may be understood on the basis of an intuitive physical picture in which removal of averaging over multiple molecules exposes the tensorial nature of Raman scattering. When an oriented single molecule gives rise to the recorded SERS spectra, the relative orientation of the molecule with respect to vector components of the local electric field determines the relative intensities of the observable vibrational states. Using a single molecule SERS framework described herein, we derive a unique molecular orientation in which a single DMS molecule is isolated at a nanojunction formed between two silver nanospheres in the 2D array. The DMS molecule is found lying nearly flat with respect to the metal surface. The derived orientation of a single molecule at a plasmonic nanojunction is consistent with observations (ii) and (iii). In particular, a careful inspection of the temporal spectral variations along the recorded single molecule SERS time sequences reveals that the time-averaged SERS backgrounds arise from individual molecular events, marked by broadened SERS

ABSTRACT Objective To determine the presence of glycosaminoglycans in the extracellular matrix of connective tissue from neoplastic and non-neoplastic colorectal tissues, since it has a central role in tumor development and progression. Methods Tissue samples from neoplastic and non-neoplastic colorectal tissues were obtained from 64 operated patients who had colorectal carcinoma with no distant metastases. Expressions of heparan sulphate, chondroitin sulphate, dermatan sulphate and their fragments were analyzed by electrospray ionization mass spectrometry, with the technique for extraction and quantification of glycosaminoglycans after proteolysis and electrophoresis. The statistical analysis included mean, standard deviation, and Student’s t test. Results The glycosaminoglycans extracted from colorectal tissue showed three electrophoretic bands in agarose gel. Electrospray ionization mass spectrometry showed characteristic disaccharide fragments from glycosaminoglycans, indicating their structural characterization in the tissues analyzed. Some peaks in the electrospray ionization mass spectrometry were not characterized as fragments of sugars, indicating the presence of fragments of the protein structure of proteoglycans generated during the glycosaminoglycan purification. The average amount of chondroitin and dermatan increased in the neoplastic tissue compared to normal tissue (p=0.01). On the other hand, the average amount of heparan decreased in the neoplastic tissue compared to normal tissue (p= 0.03). Conclusion The method allowed the determination of the glycosaminoglycans structural profile in colorectal tissue from neoplastic and non-neoplastic colorectal tissue. Neoplastic tissues showed greater amounts of chondroitin sulphate and dermatan sulphate compared to non-neoplastic tissues, while heparan sulphate was decreased in neoplastic tissues. PMID:26761548

The article describes the implementation of the methodology for determining the error search by means of the basic magnetization curve of electric cutting machines. The basic magnetization curve of the integrated operation of the electric characteristic allows one to define a fault type. In the process of measurement the definition of error calculation of the basic magnetization curve plays a major role as in accuracies of a particular characteristic can have a deleterious effect.

We conducted a comprehensive search for optical phase variations of all close-in (a/R{sub *} < 10) planet candidates in 15 quarters of Kepler space telescope data. After correcting for systematics, we found eight systems that show secondary eclipses as well as phase variations. Of these, five (Kepler-5, Kepler-6, Kepler-8, KOI-64, and KOI-2133) are new and three (TrES-2, HAT-P-7, and KOI-13) have published phase curves, albeit with many fewer observations. We model the full phase curve of each planet candidate, including the primary and secondary transits, and derive their albedos, dayside and nightside temperatures, ellipsoidal variations, and Doppler beaming. We find that KOI-64 and KOI-2133 have nightside temperatures well above their equilibrium values (while KOI-2133 also has an albedo, >1), so we conclude that they are likely to be self-luminous objects rather than planets. The other six candidates have characteristics consistent with their being planets with low geometric albedos (<0.3). For TrES-2 and KOI-13, the Kepler bandpass appears to probe atmospheric layers hotter than the planet's equilibrium temperature. For KOI-13, we detect a never-before-seen third cosine harmonic with an amplitude of 6.7 {+-} 0.3 ppm and a phase shift of -1.1 {+-} 0.1 rad in the phase curve residual, possibly due to its spin-orbit misalignment. We report derived planetary parameters for all six planets, including masses from ellipsoidal variations and Doppler beaming, and compare our results to published values when available. Our results nearly double the number of Kepler exoplanets with measured phase curve variations, thus providing valuable constraints on the properties of hot Jupiters.

Chalcogenide glasses (ChGs) are well-known for their optical properties, making them ideal candidates for emerging applications of mid-infrared microphotonic devices, such as lab-on-a-chip chemical sensing devices, which currently demand additional flexibility in processing and materials available to realize new device designs. Solution-derived processing of ChG films, initially developed in the 1980s by Chern and Lauks, has consisted mainly of spin-coating and offers unique advantages over the more traditional physical vapor deposition techniques. In the present effort, the nanoparticles of interest are luminescent quantum dots (QDs), which can be used as an on-chip source of light for a planar chemical sensing device. Prior efforts of QD incorporation have exposed limitations of spin-coating of ChG solutions, namely QD aggregation and material waste, along with incompatibility with larger scale manufacturing methods such roll-to-roll processing. This dissertation has evaluated electrospray (ES) as an alternative method of solution-derived chalcogenide glass film deposition. While employed in other materials systems, deposition of optical quality ChG films via electrospray has not been previously attempted, nor have parameters until now, been defined. This study has defined pre-cursor solution chemistry, electrospray jet process parameters required for formation of stable films, annealing protocols and resulting film attributes, yielding important correlations needed to realize high optical quality films. Electrosprayed films attributes were compared to those seen for spin coating and trade-offs in processing route and resulting quality, were identified. Optical properties of importance to device applications were defined, including surface roughness, refractive index, and infrared transmission. The use of a serpentine path of the spray over the substrate was demonstrated to obtain uniform thickness, blanket films, and demonstrates process compatibility with roll

This dissertation focused on using electrospray ionization mass spectrometry to study cluster ions and toxic metal ions in biology. In Chapter 2, it was shown that primary, secondary and quarternary amines exhibit different clustering characteristics under identical instrument conditions. Carbon chain length also played a role in cluster ion formation. In Chapters 3 and 4, the effects of solvent types/ratios and various instrumental parameters on cluster ion formation were examined. It was found that instrument interface design also plays a critical role in the cluster ion distribution seen in the mass spectrum. In Chapter 5, ESI-MS was used to investigate toxic metal binding to the [Gln11]-amyloid β-protein fragment (1-16). Pb and Cd bound stronger than Zn, even in the presence of excess Zn. Hg bound weaker than Zn. There are endless options for future work on cluster ions. Any molecule that is poorly ionized in positive ion mode can potentially show an increase in ionization efficiency if an appropriate anion is used to produce a net negative charge. It is possible that drug protein or drug/DNA complexes can also be stabilized by adding counter-ions. This would preserve the solution characteristics of the complex in the gas phase. Once in the gas phase, CID could determine the drug binding location on the biomolecule. There are many research projects regarding toxic metals in biology that have yet to be investigated or even discovered. This is an area of research with an almost endless future because of the changing dynamics of biological systems. What is deemed safe today may show toxic effects in the future. Evolutionary changes in protein structures may render them more susceptible to toxic metal binding. As the understanding of toxicity evolves, so does the demand for new toxic metal research. New instrumentation designs and software make it possible to perform research that could not be done in the past. What was undetectable yesterday will

In this paper we construct the action describing dynamics of the particle moving in curved spacetime, with a nontrivial momentum space geometry. Curved momentum space is the core feature of theories where relative locality effects are present. So far aspects of nonlinearities in momentum space have been studied only for flat or constantly expanding (de Sitter) spacetimes, relying on their maximally symmetric nature. The extension of curved momentum space frameworks to arbitrary spacetime geometries could be relevant for the opportunities to test Planck-scale curvature/deformation of particles momentum space. As a first example of this construction we describe the particle with κ-Poincaré momentum space on a circular orbit in Schwarzschild spacetime, where the contributes of momentum space curvature turn out to be negligible. The analysis of this problem relies crucially on the solution of the soccer ball problem.

Deposition of titanium dioxide (TiO{sub 2}) nanoparticles was conducted by using eletrospray method. 0.05wt% of titanium dioxide suspension was prepared and characterized by using Malvern Zetasizer prior to the experiment. From Zetasizer results, stable suspension condition was obtained which is at pH 2 with zeta potential value of ±29.0 mV. In this electrospraying, the suspension was pumped at flowrate of 5 ml/hr by using syringe pump. The input voltage of 2.1 kV was applied at the nozzle tip and counter electrode. Electrosprayed particles were collected on the grounded aluminium plate substrate which was placed at 10–20 cm from counter electrode. Particles were then characterized using FESEM and average size of electrosprayed particles obtained. Initial droplet size was calculated by scaling law and compared with FE-SEM results in order to prove droplet fission occur during electrospray. Due to the results obtained, as the working distance increase from 10–20 cm the deposited TiO{sub 2} droplet size decrease from 247–116 nm to show droplet fission occur during the experiment.

The focus of this dissertation is the use of chromatographic methods coupled with electrospray mass spectrometry (ES-MS) for the determination of both organic and inorganic compounds in aqueous solutions. The combination of liquid chromatography (LC) methods and ES-MS offers one of the foremost methods for determining compounds in complex aqueous solutions. In this work, LC-ES-MS methods are devised using ion exclusion chromatography, reversed phase chromatography, and ion exchange chromatography, as well as capillary electrophoresis (CE). For an aqueous sample, these LC-ES-MS and CE-ES-MS techniques require no sample preparation or analyte derivatization, which makes it possible to observe a wide variety of analytes as they exist in solution. The majority of this work focuses on the use of LC-ES-MS for the determination of unknown products and intermediates formed during electrochemical incineration (ECI), an experimental waste remediation process. This report contains a general introduction to the project and the general conclusions. Four chapters have been removed for separate processing. Titles are: Chapter 2: Determination of small carboxylic acids by ion exclusion chromatography with electrospray mass spectrometry; Chapter 3: Electrochemical incineration of benzoquinone in aqueous media using a quaternary metal oxide electrode in the absence of a soluble supporting electrolyte; Chapter 4: The determination of electrochemical incineration products of 4-chlorophenol by liquid chromatography-electrospray mass spectrometry; and Chapter 5: Determination of small carboxylic acids by capillary electrophoresis with electrospray mass spectrometry.

We report here using a novel technology-electrospray-assisted laser desorption ionization (ELDI)/mass spectrometry-for the rapid and sensitive detection of the major proteins that exist in dried biological fluids (e.g., blood, tears, saliva, serum), bacterial cultures, and tissues (e.g., porcine liver and heart) under ambient conditions. This technique required essentially no sample pretreatment. The proteins in the samples were desorbed using a pulsed nitrogen laser without the assistance of an organic matrix. The desorbed protein molecules were then post-ionized through their fusion into the charged solvent droplets produced from the electrospray of an acidic methanol solution; electrospray ionization (ESI) proceeded from the newly formed droplets to generate the ESI-like protein ions. This new ionization approach combines some of the features of electrospray ionization with those of matrix-assisted laser desorption ionization (MALDI), that is, sampling of a solid surface with spatial resolution, generating ESI-like mass spectra of the desorbed proteins, and operating under ambient conditions. PMID:16674100

Electrospray ionization-mass spectrometry (ESI-MS) is a powerful technique for the detection, identification, and quantification of organic compounds. As mass spectrometers have become more user-friendly and affordable, many students--often with little experience in mass spectrometry--find themselves needing to incorporate mass spectrometry into…

Some regiospecific triacylglycerol standards containing normal fatty acids, e.g., 1,3-dioleoyl-2-palmitoyl-glycerol (OPO) and 1,2-dioleoyl-3-palmitoyl-rac-glycerol (OOP), were analyzed by the electrospray ionization MS3 of their lithiated adducts. The fragment ions of the MS3 from the loss of alpha,...

HPLC fractions of diricinoleoyl-acyl-glycerols containing one non-ricinoleoyl chain from castor oil were used to identify the regiospecific location of this non-ricinoleoyl chain on glycerol backbone using electrospray ionization-MS3 of lithium adducts. The regiospecific ions used were from the loss...

Tetraacylglycerol (an acylglycerol estolide) contains an acyl chain attached to the hydroxyl group of another acyl chain attached to the glycerol backbone. Lequerolic acid (Ls, OH1420:111) is the main fatty acid in lequerella oil and can be used in industry. We have used electrospray ionization mass...

The positive ion electrospray mass spectra of the quaternary ammonium salt herbicides paraquat and diquat are examined by on-line separation with capillary electrophoresis (CE) and by direct infusion of the analytes. The analytes are separated by CE in 7-10 min at pH 3.9 in 50% m...

Electrospray ionization mass spectrometry (ESI-MS) is a powerful tool for examining the charge of proteins in solution. The charge can be manipulated through choice of solvent and pH. Furthermore, solution-accessible, protonated lysine side chains can be specifically tagged with 18-crown-6 ether to form noncovalent adducts. Chemical derivatization…

Recent developments in electrospray ionization mass spectrometry (ESI-MS) show that air amplifiers can be utilized to significantly enhance droplet desolvation and to focus gas-phase ions when provided between an electrospray (ES) source and the mass spectrometer (MS). However, these devices are bulky and expensive, which may be a factor prohibiting their broader utilization. We have developed a simple but effective method based on Bernoulli's principle, the Coanda effect and MEMS processing to focus electrosprayed droplets and liberated gas-phase ions. We demonstrate a computer simulation and fabrication process for a micromachined air amplifier. The simulation results are used to optimize the geometry and to meet performance requirements. The optimized results then provide a design guideline for the device's fabrication. The air amplifier is formed from two bonded polydimethylsiloxane (PDMS) casts. Each PDMS cast is fabricated through a molding process using a micromachined two-layer SU-8 mold. Experimental results show a 30-fold improvement in the ES current for certain operation conditions while the air amplifier is incorporated in the nano-electrospray ionization (nano-ESI) process. Compared with traditional air amplifiers, the micro-electro-mechanical systems (MEMS) based air amplifier provides good performance while keeping the fabrication process simple and cost effective.

A painted polymer part containing a conductive polymer composition containing at least one polymer and a modified graphite oxide material, which is a thermally exfoliated graphite oxide with a surface area of from about 300 sq m/g to 2600 sq m/g, wherein the painted polymer part has been electrospray painted.

A new method to interpret electrospray mass spectral data based on calculating the ratio of mass-to-charge (m/z) values of multiply charged ions is described. The mass-to-charge ratios of any two multiply charged ions corresponding to a single compound are unique numbers that enable the charge states for each ion to be unequivocally identified. The multiply charged ions in electrospray mass spectra originate from the addition or abstraction of protons, cations, or anions to and from a compound under analysis. In contrast to existing deconvolution processes, the charge ratio analysis method (CRAM), identifies the charge states of multiply charged ions without any prior knowledge of the nature of the charge-carrying species. In the case of high-resolution electrospray mass spectral data, in which multiply charged ions are resolved to their isotopic components, the CRAM is capable of correlating the isotope peaks of different multiply charged ions that share the same isotopic composition. This relative ratio method is illustrated here for electrospray mass spectral data of lysozyme and oxidized ubiquitin recorded at low- to high-mass resolution on quadrupole ion trap and Fourier transform ion cyclotron mass spectrometers, and theoretical data for the protein calmodulin based upon a reported spectrum recorded on the latter. PMID:15623285

An electrodynamic ion funnel has been developed for improving the sensitivity of electrospray ionization sources widely used in the mass spectrometric study of proteins and other biological macromolecules. The ion funnel consists of 52 electrodes and works under the combined influence of RF and DC voltages in the pressure range of 0.1 to 5 mbar. A novel feature of this ion funnel is the specific shape of the exit electrode that improves transmission of lower mass ions by reducing the depth of effective trapping potentials. In this paper, we report on the optimization of the ion funnel design using ion trajectory simulation software SIMION 8.0 especially in the mass range 500–5000 amu, followed by experimental observations of the ion transmission from the electrospray interface. It is seen that the electrospray-ion funnel combination greatly enhances the transmission when compared with an electrospray-skimmer interface. Ion currents > 1 nA could be obtained at the exit of the ion funnel for dilute Streptomycin Sulphate (~ 1500 amu) solution with the ion funnel operating in the 500–900 kHz frequency range, amplitude of 70 Vp‑p, under a DC gradient of about 20 Volts/cm at a background pressure of 0.3 mbar. Details of the construction of the ion funnel along with the experimental results are presented.

A heated capillary inlet for an electrospray ionization mass spectrometry (ESI-MS) interface was compared with shorter versions of the inlet to determine the effects on transmission and ionization efficiencies for low-flow (nano) electrosprays. Five different inlet lengths were studied, ranging from 6.4 to 1.3 cm. As expected, the electrospray current transmission efficiency increased with decreasing capillary length due to reduced losses to the inside walls of the capillary. This increase in transmission efficiency with shorter inlets was coupled with reduced desolvation of electrosprayed droplets. Surprisingly, as the inlet length was decreased, some analytes showed little or no increase in sensitivity, while others showed as much as a15 – fold gain. The variation was shown to beat least partially correlated with analyte mobilities, with the largest gains observed for higher mobility species, but also affected by solution conductivity, flow rate, and inlet temperature. Strategies for maximizing sensitivity while minimizing biases in ion transmission through the heated capillary interface are proposed. PMID:19815425

HPLC fractions of castor oil were used to identify the regiospecific location of non-hydroxyl fatty acids on glycerol backbone in diricinoleoyl-acyl-glycerols using electrospray ionization MS3 of lithium adducts. The regiospecific ions in MS3 spectra were from the loss of 'a,B'-unsaturated fatty aci...

A method of regiospecific analysis of triacylglycerols (TAG) in vegetable oils and animal fats is reported here using the electrospray ionization MS3 of TAG lithiated adducts. The fragment ions of the MS3 from the loss of fatty acids at the sn-2 position as alpha, Beta-unsaturated fatty acids were u...

Active systems have proved to be very sensitive to the geometry of their environment. This is often achieved by spending significant time at the boundary, probing its shape by gliding along it. I will discuss coarse graining the microscopic dynamics of self-propelled particles on a general curved surface to predict the way the density profile on the surface depends on its geometry. Beyond confined active particles, this formalism is a natural starting point to study objects that cannot leave the boundary at all, such as cells crawling on a curved substrate, animals running on uneven ground, or active colloids trapped at an interface.

A common problem in hydrology is to fit a smooth curve to cyclic or periodic data, either to define the most probable values of the data or to test some principle that one wishes to demonstrate. This study treats of those problems where the length or period of the cycle is know beforehand - as a day, year, or meander length for example. Curve-fitting can be made by free-hand drawing, and where the data are closely aligned this method offers the simplest and most direct course. However, there are many problems where the best fit is far from obvious, and analytical methods may be necessary.

Performance curves of the NEXT thruster are highly important in determining the thruster's ability in performing towards mission-specific goals. New performance curves are proposed and examined here. The Evolutionary Mission Trajectory Generator (EMTG) is used to verify variations in mission solutions based on both available thruster curves and the new curves generated. Furthermore, variations in BOL and EOL curves are also examined. Mission design results shown here validate the use of EMTG and the new performance curves.

An essential concern in the application of any equating procedure is determining whether tests can be considered equated after the tests have been placed onto a common scale. This article clarifies one equating criterion, the first-order equity property of equating, and develops a new method for evaluating equating that is linked to this…

Visualization experiments employing rectangular cross-section curved channels were performed in order to examine the fundamental characteristics of a curved detonation wave propagating stably through an annular channel. A stoichiometric ethylene-oxygen mixture gas and five types of curved channels with different inner radii of curvature were used. The detonation waves propagating in the curved channels were curved due to the expansion waves from the inner walls of the curved channels. The ratio of the inner radius of curved channel (ri) to the normal detonation cell width (λ) was an important factor determining the stability of the curved detonation waves. The detonation propagation mode in the curved channels transitioned from unstable to stable in the range 14 ≤ ri/λ ≤ 26. The normal detonation velocity (Dn) of the curved detonation wave propagating stably in a curved channel was approximately formulated. The approximated Dn given by the formula agreed well with the experimental results. The front shock shape of the curved detonation wave could be reconstructed accurately using the formula. The value of Dn nondimensionalized by the Chapman-Jouguet detonation velocity became a function of the local curvature of the curved detonation wave (κ) nondimensionalized by λ regardless of the shape of curved channel. The front shock shapes of the detonation waves in the stable mode became similar to each other under constant ri/λ conditions.

The NRCS Curve Number (known also as SCS-CN) method is well known as a tool in predicting flood runoff depth from small ungauged catchment. The traditional way of determination the CNs, based on soil characteristics, land use and hydrological conditions, seemed to have tendency to overpredict the floods in some cases. Over 30 year rainfall-runoff data, collected in two small (A=23.4 & 82.4 km2), lowland, agricultural catchments in Center of Poland (Banasik & Woodward 2010), were used to determine runoff Curve Number and to check a tendency of changing. The observed CN declines with increasing storm size, which according recent views of Hawkins (1993) could be classified as a standard response of watershed. The analysis concluded, that using CN value according to the procedure described in USDA-SCS Handbook one receives representative value for estimating storm runoff from high rainfall depths in the analyzes catchments. This has been confirmed by applying "asymptotic approach" for estimating the watershed curve number from the rainfall-runoff data. Furthermore, the analysis indicated that CN, estimated from mean retention parameter S of recorded events with rainfall depth higher than initial abstraction, is also approaching the theoretical CN. The observed CN, ranging from 59.8 to 97.1 and from 52.3 to 95.5, in the smaller and the larger catchment respectively, declines with increasing storm size, which has been classified as a standard response of watershed. The investigation demonstrated also changeability of the CN during a year, with much lower values during the vegetation season. Banasik K. & D.E. Woodward (2010). "Empirical determination of curve number for a small agricultural watrshed in Poland". 2nd Joint Federal Interagency Conference, Las Vegas, NV, June 27 - July 1, 2010 (http://acwi.gov/sos/pubs/2ndJFIC/Contents/10E_Banasik_ 28_02_10. pdf). Hawkins R. H. (1993). "Asymptotic determination of curve numbers from data". Journal of Irrigation and Drainage

I investigate phase-ordering kinetics on static curved surfaces, starting from a well-known time-dependent Ginzburg-Landau equation, known as model A and valid in flat two-dimensional systems, and generalizing this to apply on curved surfaces. I develop and implement an interface formalism for model A, valid in both curved and flat surfaces. This is based on an interface velocity equation explicitly showing how interface motion couples to local surface geometry. I discuss extensively both theoretical and numerical aspects of this formalism. I derive a coupled set of curvature equations and use them to obtain an approximate expression for the curvature autocorrelation function (CAF) in the flat case. This is compared for the first time to numerical simulation results and shows that the CAF provides dynamical information not readily available from the traditional order-parameter structure-factor, yet is far easier to compute than the latter. A dominant length-scale is observed for the first time, in the domain interface undulations, even in Euclidean model A dynamics. I discuss how this affects the interpretation of what is needed for a system to exhibit dynamical scaling. I look at the effect of surface Gauss curvature on the growth rate of domains and show that when the phase-ordering occurs on a corrugated surface, metastable long-range disorder may result. I show how these effects cause a break-down of dynamical scaling and power-law growth, how they bring about the elimination of the zero-temperature fixed point of Euclidean model A, and how phase-ordering in curved lipid-bilayer membranes should be affected. A new very-late stage regime appears for simulations of model A on sinusoid (i.e. egg-carton-like) surfaces. These features indicate that thermal noise should be included in future studies of phase ordering kinetics on curved surfaces. They also indicate that even before the order-parameter is explicitly coupled to surface quantities such as the local mean

Supply curves of conserved energy provide an accounting framework that expresses the potential for energy conservation. The economic worthiness of a conservation measure is expressed in terms of the cost of conserved energy, and a measure is considered economical when the cost of conserved energy is less than the price of the energy it replaces. A supply curve of conserved energy is independent of energy prices; however, the economical reserves of conserved energy will depend on energy prices. Double-counting of energy savings and error propagation are common problems when estimating conservation potentials, but supply curves minimize these difficulties and make their consequences predictable. The sensitivity of the cost of conserved energy is examined, as are variations in the optimal investment strategy in response to changes in inputs. Guidelines are presented for predicting the consequences of such changes. The conservation supply curve concept can be applied to peak power, water, pollution, and other markets where consumers demand a service rather than a particular good.

Two points determine a line. Three noncollinear points determine a quadratic function. Four points that do not lie on a lower-degree polynomial curve determine a cubic function. In general, n + 1 points uniquely determine a polynomial of degree n, presuming that they do not fall onto a polynomial of lower degree. The process of finding such a…

We identify a previously undetected link between the river network morphology and key recession curves properties through a conceptual-physical model of the drainage process of the riparian unconfined aquifer. We show that the power-law exponent, α, of -dQ/dt vs. Q curves is related to the power-law exponent of N(l) vs. G(l) curves (which we show to be connected to Hack's law), where l is the downstream distance from the channel heads, N(l) is the number of channel reaches exactly located at a distance l from their channel head, and G(l) is the total length of the network located at a distance greater or equal to l from channel heads. Using Digital Terrain Models and daily discharge observations from 67 US basins we find that geomorphologic α estimates match well the values obtained from recession curves analyses. Finally, we argue that the link between recession flows and network morphology points to an important role of low-flow discharges in shaping the channel network.

THIS BOOKLET, ONE OF A SERIES, HAS BEEN DEVELOPED FOR THE PROJECT, A PROGRAM FOR MATHEMATICALLY UNDERDEVELOPED PUPILS. A PROJECT TEAM, INCLUDING INSERVICE TEACHERS, IS BEING USED TO WRITE AND DEVELOP THE MATERIALS FOR THIS PROGRAM. THE MATERIALS DEVELOPED IN THIS BOOKLET INCLUDE SUCH CONCEPTS AS (1) SIMPLE CLOSED CURVES, (2) NETWORKS, (3) MAP…

Miniature cameras for consumer electronics and mobile phones have been, and continue to be, in fast development. The system level requirements, such as manufacturing cost, packaging, and sensor characteristics, impose unique challenges for optical designers. In this paper, we discuss the potential optical benefits of having a curved image surface rather than a flat one. We show that curved sensor technology allows for optically faster lens solutions. We discuss trade-offs of several relevant characteristics, such as packaging, chief ray angle, image quality, and tolerance sensitivity. A comparison of a benchmark flat field lens, and an evaluation design imaging on a curved surface and working at f/1.6, provides useful specific insights. For a given image quality, departing from a flat imaging surface does not allow significantly reducing the total length of a lens. PMID:26479656

We survey algorithms for computing isogenies between elliptic curves defined over a field of characteristic either 0 or a large prime. We introduce a new algorithm that computes an isogeny of degree ell ( ell different from the characteristic) in time quasi-linear with respect to ell E This is based in particular on fast algorithms for power series expansion of the Weierstrass wp -function and related functions.

The objective of this study was to determine why the United States has experienced a higher rate of unemployment in the post-war period than other countries at similar stages of development. The study reviewed the Phillips Curve Theory--the theory underlying wage and price changes--and the development and post-war characteristics of labor market…

Most geometric modeling systems use either polynomial or rational functions to represent geometry. In such systems most computational problems can be formulated as systems of polynomials in one or more variables. Classical elimination theory can be used to solve such systems. Here Cayley's method of elimination is summarized and it is shown how it can best be used to solve the curve/curve intersection problem. Cayley's method was found to be a more straightforward approach. Furthermore, it is computationally simpler, since the elements of the Cayley matrix are one variable instead of two variable polynomials. Researchers implemented and tested both methods and found Cayley's to be more efficient. Six pairs of curves, representing mixtures of lines, circles, and cubic arcs were used. Several examples had multiple intersection points. For all six cases Cayley's required less CPU time than the other method. The average time ratio of method 1 to method 2 was 3.13:1, the least difference was 2.33:1, and the most dramatic was 6.25:1. Both of the above methods can be extended to solve the surface/surface intersection problem.

Zinc sulfate (ZnSO4) is a common salt present in oxidized surface waters and may serve as a suitable model material to better understand precipitation/nucleation processes in aqueous fluids. In brief, precipitation of ZnSO4 commences with single molecule association (complexation) reactions and proceeds via a wide range of prenucleation clusters (ZnSO4)n and nanocrystalites ultimately toward bulk ZnSO4. Evidently, ZnSO4 growth will pass through the cluster-size domain, from which small ZnSO4 cluster subunits emerge with characteristic chain, sheet and 3-D structures. This experimental study focuses on small zinc sulfate clusters and provides a set of preliminary results pertaining to the stoichiometry, abundance and stability of these materials in aqueous environments. At present, very little is known with respect to the composition, structure and stability of ZnSO4 at the cluster level, however, electrospray ionization (ESI) mass spectrometry can provide detailed insight into the aforementioned features of ZnSO4. In addition, application of resonance techniques, such as high-resolution Fourier Transfer Ion Cyclotron Resonance Mass Spectrometry (FT-ICR/MS) provides detailed information with respect to the molecular composition of individual ion clusters at high resolution. Here we present the stoichiometries of zinc sulfate ion clusters identified using FT-ICR/MS. In 15mM dilute aqueous solution of zinc sulfate, singly-charged ion clusters [Znm(SO4)m-1(OH)●(H2O)n]+ with m=2, 3, 4 and 5 have been identified. In addition, a set of doubly-charged clusters with the general form [Znm(SO4)m-1●(H2O)n]2+ with 4≤m≤10 have been characterized. We will propose a scheme, in which singly-charged cluster species with m=4,5 are regarded to be of a critical-size from which stable doubly-charged ions begin to emerge. Upon passing the m~4-5 size-range, zinc sulfate clusters exhibit a strong affinity towards water with stable hepta-hydrates marking the upper range of

Negative ion desorption electrospray ionization (DESI) was used for the analysis of an ex vivo tissue sample set comprising primary colorectal adenocarcinoma samples and colorectal adenocarcinoma liver metastasis samples. Frozen sections (12 μm thick) were analyzed by means of DESI imaging mass spectrometry (IMS) with spatial resolution of 100 μm using a computer-controlled DESI imaging stage mounted on a high resolution Orbitrap mass spectrometer. DESI-IMS data were found to predominantly feature complex lipids, including phosphatidyl-inositols, phophatidyl-ethanolamines, phosphatidyl-serines, phosphatidyl-ethanolamine plasmalogens, phosphatidic acids, phosphatidyl-glycerols, ceramides, sphingolipids, and sulfatides among others. Molecular constituents were identified based on their exact mass and MS/MS fragmentation spectra. An identified set of molecules was found to be in good agreement with previously reported DESI imaging data. Different histological tissue types were found to yield characteristic mass spectrometric data in each individual section. Histological features were identified by comparison to hematoxylin-eosin stained neighboring sections. Ions specific to certain histological tissue types (connective tissue, smooth muscle, healthy mucosa, healthy liver parenchyma, and adenocarcinoma) were identified by semi-automated screening of data. While each section featured a number of tissue-specific species, no potential global biomarker was found in the full sample set for any of the tissue types. As an alternative approach, data were analyzed by principal component analysis (PCA) and linear discriminant analysis (LDA) which resulted in efficient separation of data points based on their histological types. A pixel-by-pixel tissue identification method was developed, featuring the PCA/LDA analysis of authentic data set, and localization of unknowns in the resulting 60D, histologically assigned LDA space. Novel approach was found to yield results which are

A high speed curved position sensitive porportional counter detector for use in x-ray diffraction, the detection of 5-20 keV photons and the like. The detector employs a planar anode assembly of a plurality of parallel metallic wires. This anode assembly is supported between two cathode planes, with at least one of these cathode planes having a serpentine resistive path in the form of a meander having legs generally perpendicular to the anode wires. This meander is produced by special microelectronic fabrication techniques whereby the meander "wire" fans outwardly at the cathode ends to produce the curved aspect of the detector, and the legs of the meander are small in cross-section and very closely spaced whereby a spatial resolution of about 50 .mu.m can be achieved. All of the other performance characteristics are about as good or better than conventional position sensitive proportional counter type detectors. Count rates of up to 40,000 counts per second with 0.5 .mu.s shaping time constants are achieved.

We compute the optical conductivity for an out-of-plane deformation in graphene using an approach based on solutions of the Dirac equation in curved space. Different examples of periodic deformations along one direction translates into an enhancement of the optical conductivity peaks in the region of the far- and mid-infrared frequencies for periodicities ∼100 nm. The width and position of the peaks can be changed by dialling the parameters of the deformation profiles. The enhancement of the optical conductivity is due to intraband transitions and the translational invariance breaking in the geometrically deformed background. Furthermore, we derive an analytical solution of the Dirac equation in a curved space for a general deformation along one spatial direction. For this class of geometries, it is shown that curvature induces an extra phase in the electron wave function, which can also be explored to produce interference devices of the Aharonov-Bohm type. PMID:24759188

We present a computational study of the transport properties of campylotic (intrinsically curved) media. It is found that the relation between the flow through a campylotic media, consisting of randomly located curvature perturbations, and the average Ricci scalar of the system, exhibits two distinct functional expressions, depending on whether the typical spatial extent of the curvature perturbation lies above or below the critical value maximizing the overall scalar of curvature. Furthermore, the flow through such systems as a function of the number of curvature perturbations is found to present a sublinear behavior for large concentrations, due to the interference between curvature perturbations leading to an overall less curved space. We have also characterized the flux through such media as a function of the local Reynolds number and the scale of interaction between impurities. For the purpose of this study, we have also developed and validated a new lattice Boltzmann model. PMID:24173367

We have applied the close binary system analysis package WINFITTER to a variety of exoplanet transiting light curves taken both from the NASA Exoplanet Archive and our own ground-based observations. WINFitter has parameter options for a realistic physical model, including gravity brightening and structural parameters derived from Kopal's applications of the relevant Radau equation, and it includes appropriate tests for determinacy and adequacy of its best fitting parameter sets. We discuss a number of issues related to empirical checking of models for stellar limb darkening, surface maculation, Doppler beaming, microvariability, and transit time variation (TTV) effects. The Radau coefficients used in the light curve modeling, in principle, allow structural models of the component stars to be tested.

A discrete-time quantum walk (QW) is essentially a unitary operator driving the evolution of a single particle on the lattice. Some QWs admit a continuum limit, leading to familiar PDEs (e.g., the Dirac equation). In this paper, we study the continuum limit of a wide class of QWs and show that it leads to an entire class of PDEs, encompassing the Hamiltonian form of the massive Dirac equation in (1+1) curved spacetime. Therefore, a certain QW, which we make explicit, provides us with a unitary discrete toy model of a test particle in curved spacetime, in spite of the fixed background lattice. Mathematically, we have introduced two novel ingredients for taking the continuum limit of a QW, but which apply to any quantum cellular automata: encoding and grouping.

There are several common conventions in use by the gravitational-wave community to describe the amplitude of sources and the sensitivity of detectors. These are frequently confused. We outline the merits of and differences between the various quantities used for parameterizing noise curves and characterizing gravitational-wave amplitudes. We conclude by producing plots that consistently compare different detectors. Similar figures can be generated on-line for general use at http://rhcole.com/apps/GWplotter.

Nearly 15% of the known exoplanet population have significantly eccentric orbits (e > 0.25). Systems with planets on highly eccentric orbits provide natural laboratories to test theories of orbital evolution, tidal forcing, and atmospheric response. The two best studied eccentric exoplanets are HAT-P-2b (e~0.5) and HD 80606 b (e~0.9). Both of these eccentric planets have full or partial orbit phase curve observations taken with the 3.6, 4.5, and 8.0 micron channels of the Spitzer IRAC instrument. These phase-curve observations of HAT-P-2b and HD 80606 b have given us important insights into atmospheric radiative timescales, planetary rotation rates and orbital evolution, and planet-star tidal interactions. Here I will overview the key results from the Spitzer observational campaigns for HAT-P-2b and HD 80606 b and look toward the future of phase curve observations of eccentric exoplanets in the era of JWST.

Growth curves for children with Laron syndrome were constructed on the basis of repeated measurements made throughout infancy, childhood, and puberty in 24 (10 boys, 14 girls) of the 41 patients with this syndrome investigated in our clinic. Growth retardation was already noted at birth, the birth length ranging from 42 to 46 cm in the 12/20 available measurements. The postnatal growth curves deviated sharply from the normal from infancy on. Both sexes showed no clear pubertal spurt. Girls completed their growth between the age of 16-19 years to a final mean (SD) height of 119 (8.5) cm whereas the boys continued growing beyond the age of 20 years, achieving a final height of 124 (8.5) cm. At all ages the upper to lower body segment ratio was more than 2 SD above the normal mean. These growth curves constitute a model not only for primary, hereditary insulin-like growth factor-I (IGF-I) deficiency (Laron syndrome) but also for untreated secondary IGF-I deficiencies such as growth hormone gene deletion and idiopathic congenital isolated growth hormone deficiency. They should also be useful in the follow up of children with Laron syndrome treated with biosynthetic recombinant IGF-I. PMID:8333769

This report presents a comprehensive spectral analysis of common bacterial phospholipids using electrospray/mass spectrometry (ESI/MS) under both negative and positive ionization conditions. Phospholipids under positive ionization yield sodium-adduct molecular ions which are mos...

An on-column metal coating procedure was developed for sheathless electrospray emitters, based on Justus von Liebig's electroless silver mirror reaction followed by electrochemical deposition of gold onto the silver layer. The coating procedure is straightforward, mild, inexpensive, and can be performed with standard laboratory equipment. A long-term (600 h) stability investigation of the conductive coating was carried out by continuous electrospray in the positive electrospray mode, and no degradation in performance was found. The simplicity of the coating procedure and the robustness of the spray tips makes the spray tips highly suitable to couple delicate wall-coated or monolithic capillary columns to mass spectrometry. Peptide mixtures were separated by capillary electrophoresis and injected into either a Hadamard-transform time-of-flight mass analyzer or a commercial quadrupole mass analyzer using the described sheathless electrospray emitters. The performance was judged to be excellent. PMID:15759300

Context. Clouds have been shown to be present in many exoplanetary atmospheres. Cloud formation modeling predicts considerable inhomogeneities of cloud cover, consistent with optical phase curve observations. However, optical phase curves cannot resolve some existing degeneracies between cloud location and cloud optical properties. Aims: We present a conceptually simple technique for detecting inhomogeneous cloud cover on exoplanets. Such an inhomogeneous cloud cover produces an asymmetric primary transit of the planet in front of the host star. Asymmetric transits produce characteristic residuals that are different from standard symmetric models. Furthermore, bisector spans can be used to determine asymmetries in the transit light curve. Methods: We apply a model of asymmetric transits to the light curves of HAT-P-7b, Kepler-7b, and HD 209458b and search for possible cloud signatures. The nearly uninterrupted Kepler photometry is particularly well suited for this method since it allows for a very high time resolution. Results: We do not find any statistically sound cloud signature in the data of the considered planets. For HAT-P-7b, a tentative detection of an asymmetric cloud cover is found, consistent with analysis of the optical phase curve. Based on Bayesian probability arguments, a symmetric model with an offset in the transit ephemeris is still the most viable model. This work demonstrates that for suitable targets, namely low-gravity planets around bright stars, the method can be used to constrain cloud cover characteristics and is thus a helpful additional tool for the study of exoplanetary atmospheres.

The presence of sulfonamide (SA) residues in foods is largely due to the raising of animals with sulfonamide antibiotics added or polluted feedstuff. Because of interference from the matrices, the commonly used immunoassay or chromatographic method is not suitable for the analysis of multi-SAs in feedstuff. A high performance liquid chromatographic-electrospray tandem mass spectrometric (HPLC/ESI-MS-MS) method has been established for the simultaneous determination of multi-SAs including sulfadiazine (SD), sulfapyridine (SPD), sulfamerazine (SM1), sulfameter (SM), sulfamethazine (SM2), sulfamethoxypyridazine (SMP), sulfamethoxazole (SMZ), sulfamonomethoxine (SMM), sulfadimethoxine (SDM) and sulfaquinoxaline (SQX). After solvent extraction, solid phase extraction, dilution and reversed-phase HPLC separation, SAs were detected by ESI-MS-MS under multi-reaction monitoring mode. The qualification analysis was done by using retention time and distribution of diagnostic ion pairs, and the quantification was based on the peak intensity of common fragment ion m/z 156. The limits of quantification for 10 SAs were 0.5 - 2.0 microg/kg (S/N = 10). The correlation coefficient of linear calibration curve was over 0.9995 within the SAs concentration range 2.0 - 200 microg/L except for SDM and SQX. At the spiked level of 1.0 mg/kg, the average recoveries for the 10 SAs were between 70% and 92%, the relative standard deviations were under 10% for intra-day and under 15% for inter-day. Routine tests showed the method was fast, sensitive, specific, and practical for the SAs determination in feedstuff. PMID:16250451

Azilsartan medoxomil (AZM), an ester prodrug of azilsartan (AZ), and chlorthalidone (CLT) have recently been approved as a combination therapy for the management of hypertension. This is the first report which described a selective and sensitive method for the simultaneous quantification of AZ and CLT in rat and human plasma using liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). AZ and CLT were extracted from plasma by liquid-liquid extraction technique and separated on a C18 reverse phase column using ammonium acetate (10mM, pH 4)-mixture of methanol and acetonitrile (8:92, v/v) as a mobile phase at a flow rate of 0.7mL/min. Detection was performed by electrospray ionization (ESI) operated in negative multiple reaction monitoring (MRM) mode. The lower limit of quantitation (LLOQ) of this method was 1ng/mL and the calibration curves were linear (r(2)≥0.995) over the concentration range of 1-4000ng/mL for both the analytes. The intra- and inter-day precision and accuracy were well within the acceptable limits. The mean extraction recoveries were found to be about 80% and no matrix effect was observed. AZ and CLT were found to be stable under all relevant storage conditions. The method was successfully applied to the oral pharmacokinetic study of AZM and CLT in rats. Further, the sensitivity of the method enabled the determination of protein binding of AZ and CLT in human plasma. PMID:25899870

The opioid partial agonist medication, buprenorphine (BUP), and its primary metabolite, norbuprenorphine (NBUP), are extensively glucuronidated. Sensitive analytical methods that include determination of buprenorphine-3-glucuronide (BUPG) and norbuprenorphine-3-glucuronide (NBUPG) are needed to more fully understand the metabolism and pharmacokinetics of buprenorphine. A method has now been developed that uses solid-phase extraction followed by liquid chromatography-electrospray ionization-tandem mass spectrometry. BUP-d4, NBUP-d3, and morphine-3-glucuronide-d3 were used as internal standards. The lower limit of quantitation was 0.1 and 0.5 ng/mL for each of the analytes in 1-mL of human plasma and urine, respectively, except for NBUP in urine in which it was 2.5 ng/mL. The analytes were stable under the following conditions: plasma and urine at room temperature, up to 20 hours; plasma and urine at -20 degrees C for 119 and 85 days, respectively; plasma freeze-thaw, up to 3 cycles; processed sample, up to 96 hours at -20 degrees C and up to 48 hours on the autosampler; stock solutions at room temperature and at -20 degrees C, up to 6 hours and 128 days, respectively. In plasma collected from 5 subjects on maintenance daily sublingual doses of 16 mg BUP and 4 mg naloxone, respective 0- to 24-hour areas under the curve were 32, 88, 26, and 316 ng/mL x h for BUP, NBUP, BUPG, and NBUPG. In urine samples respective percent of daily dose excreted in the 24-hour urine were 0.014%, 1.89%, 1.01%, and 7.76%. This method allowed us to determine that NBUPG is a major metabolite present in plasma and urine of BUP. Because urinary elimination is limited ( approximately 11% of daily dose), the role of NBUPG in total clearance of buprenorphine is not yet known. PMID:16628138

Laser-induced breakdown spectroscopy (LIBS) is characterized as a powerful tool in in-situ online analysis with its fast and multiple detecting abilities. But in the area of detecting trace sample in aqueous solution of low concentration, the turbulence, scattering, absorbance and cooling effect of liquid medium limits its performance. Traditional method includes liquid jet, liquid-solid transformation and pre-concentration on other medium, yet the procedure of sample preparation is complicated and time consuming. In this work, we propose a new method to achieve pre-concentration, in which filter paper and electro-spray ionization (ESI) are used. In our experiment, we choose MnSO4 as sample. The surface of filter paper is sprayed with MnSO4 aqueous solution of different concentration by an ESI. The pulsed laser is focused on the surface of filter paper and the plasma is formed in the focusing area. Through an optical fiber the spectrum of plasma is detected by a spectrometer. The ESI system, pulses generator system and the UI on PC are home-made. The spectra lines of Mn at 257.6nm, 259.4nm and 260.6nm are analyzed. Results show that the limit of detection at 257.6nm is sub-ppb and the R2 of calibration curve is more than 0.93. Compared with traditional method, like soak and drip processing, our method can increase the concentration of the sample by simply expanding spraying time, achieving a higher signal-to-noise ratio (SNR) and a lower limit of detection (LOD). In addition, the consumption of sample solution is as low as several hundred μl in each detection.

We describe a simple stable isotope dilution method for accurate determination of S-adenosylmethionine (SAM) and S-adenosylhomocysteine (SAH) in plasma as a diagnostic test. SAM and SAH are key metabolic intermediates of methionine metabolism and the methylation cycle. Determination of SAM and SAH in plasma was performed by high performance liquid chromatography coupled with electrospray positive ionization tandem mass spectrometry (HPLC-ESI-MS/MS). Calibrators (SAM and SAH) and internal standards ((2)H3-SAM and (2)H4-SAH) were included in each analytical run for calibration. Sample preparation involved combining 20 μL sample with 180 μL of internal standard solution consisting of heavy isotope labeled internal standards in mobile phase A and filtering by ultracentrifugation through a 10 kd MW cutoff membrane. Sample filtrate (3 μL) was injected by a Shimadzu Nexera LC System interfaced with a 5500 QTRAP(®) (AB Sciex). Chromatographic separation was achieved on a 250 mm × 2.0 mm EA:faast column from Phenomenex. Samples were eluted at a flow rate of 0.20 mL/min with a binary gradient with a total run time of 10 min. The source operated in positive ion mode at an ion spray voltage of +5000 V. SAM and SAH resolved by a gradient to 100 % methanol with retention times of 6.0 and 5.7 min, respectively. The observed m/z values of the fragment ions were m/z 399 → 250 for SAM, m/z 385 → 136 for SAH, m/z 402 → 250 for (2)H3-SAM, m/z 203 → 46. The calibration curve was linear over the ranges of 12.5-5000 nmol/L for SAM and SAH. PMID:26602137

Direct analysis of silica C(18)-coated solid-phase microextraction (SPME) fibers using desorption electrospray ionization mass spectrometry (DESI-MS) for the purpose of analyzing drugs from raw urine is presented. The method combines a simple, inexpensive, and solvent-less sample preparation technique with the specificity and speed of DESI-MS and MS/MS. Extraction of seven drugs from raw urine is performed using specially designed SPME fibers coated uniformly with silica-C(18) stationary phase. Each SPME device is inserted into unprocessed urine under gentle agitation and, then, removed, rinsed, and analyzed directly by DESI-MS (MS/MS). Rapid screening over a wide mass range is afforded by coupling the method with a time of flight (TOF) mass spectrometer while quantitative analysis is performed using selected reaction monitoring (SRM) using a triple quadrupole mass spectrometer. The performance of the SPME DESI-MS/MS method was evaluated by preparing calibration standards and quality control (QC) samples of the seven drug compounds from urine over a range from 20 to 1000 ng/mL, with the exception of meprobamate which was prepared from 200 to 10000 ng/mL. The calibration curves constructed for each analyte had an R(2) > 0.99. The range of precision (%CV) and accuracy values (% bias) for low QC samples was 1-11% and 3-38%, respectively. Precision and accuracy values for high QC samples range from 0.9 to 8% and -31 to -8%. Results from urine specimens of actual exposure to drugs screened using the SPME DESI-MS/MS method showed good agreement with the conventional immunoassays and GC/MS analysis. Liquid desorption of the SPME fiber followed by LC/MS/MS also showed good agreement with the SPME DESI-MS/MS method. PMID:20695439

This paper presents the application of ultra-high performance LC (UHPLC) and MS for the determination of 151 pesticides in soybeans and pulses. A core-shell particle (2.6 micro m particle size) column and a fully porous sub-2 microm (1.7 microm particle size) column showed comparable performance in chromatographic resolution and separation, increasing selectivity, and reducing analysis time. UHPLC was coupled with either a triple quadrupole mass analyzer (MS/MS) or a quadrupole Orbitrap (namely Orbital trap) mass spectrometer (Q-Orbitrap MS), which possesses fast data acquisition capability. Both configurations yielded analytical run times of < or =14 min. Soybean and pulse samples were analyzed and quantitated for pesticide residues using the QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) procedure, UHPLC/electrospray ionization (ESI)-MS/MS, and matrix-matched standard calibration curves (in an analytical range of 5-500 microg/kg) with isotopically-labeled standards or a chemical analog as internal standards. The method performance parameters that included overall recovery, intermediate precision, and measurement uncertainty were evaluated according to a nested design experiment. Approximately 89% of the pesticides studied had recoveries between 81 and 110%; 95%, had intermediate precision < or =20%; and 93% showed measurement uncertainty < or =40%. From a pilot study of 100 samples, eight tested positive by UHPLCIESI-MS/MS for carbendazim, methomyl, or imidacloprid. These pesticides were further confirmed using UHPLC/ESI-Q-Orbitrap MS based on accurate mass measurement with mass error < or =5 ppm. PMID:24282957

The detection of bacterial-specific volatile metabolites may be a valuable tool to predict infection. Here we applied a real-time mass spectrometric technique to investigate differences in volatile metabolic profiles of oral bacteria that cause periodontitis. We coupled a secondary electrospray ionization (SESI) source to a commercial high-resolution mass spectrometer to interrogate the headspace from bacterial cultures and human saliva. We identified 120 potential markers characteristic for periodontal pathogens Aggregatibacter actinomycetemcomitans (n = 13), Porphyromonas gingivalis (n = 70), Tanerella forsythia (n = 30) and Treponema denticola (n = 7) in in vitro cultures. In a second proof-of-principle phase, we found 18 (P. gingivalis, T. forsythia and T. denticola) of the 120 in vitro compounds in the saliva from a periodontitis patient with confirmed infection with P. gingivalis, T. forsythia and T. denticola with enhanced ion intensity compared to two healthy controls. In conclusion, this method has the ability to identify individual metabolites of microbial pathogens in a complex medium such as saliva.

The detection of bacterial-specific volatile metabolites may be a valuable tool to predict infection. Here we applied a real-time mass spectrometric technique to investigate differences in volatile metabolic profiles of oral bacteria that cause periodontitis. We coupled a secondary electrospray ionization (SESI) source to a commercial high-resolution mass spectrometer to interrogate the headspace from bacterial cultures and human saliva. We identified 120 potential markers characteristic for periodontal pathogens Aggregatibacter actinomycetemcomitans (n = 13), Porphyromonas gingivalis (n = 70), Tanerella forsythia (n = 30) and Treponema denticola (n = 7) in in vitro cultures. In a second proof-of-principle phase, we found 18 (P. gingivalis, T. forsythia and T. denticola) of the 120 in vitro compounds in the saliva from a periodontitis patient with confirmed infection with P. gingivalis, T. forsythia and T. denticola with enhanced ion intensity compared to two healthy controls. In conclusion, this method has the ability to identify individual metabolites of microbial pathogens in a complex medium such as saliva. PMID:26477831

Summary The ROC (Receiver Operating Characteristic) curve is the most commonly used statistical tool for describing the discriminatory accuracy of a diagnostic test. Classical estimation of the ROC curve relies on data from a simple random sample from the target population. In practice, estimation is often complicated due to not all subjects undergoing a definitive assessment of disease status (verification). Estimation of the ROC curve based on data only from subjects with verified disease status may be badly biased. In this work we investigate the properties of the doubly robust (DR) method for estimating the ROC curve under verification bias originally developed by Rotnitzky et al. (2006) for estimating the area under the ROC curve. The DR method can be applied for continuous scaled tests and allows for a non ignorable process of selection to verification. We develop the estimator's asymptotic distribution and examine its finite sample properties via a simulation study. We exemplify the DR procedure for estimation of ROC curves with data collected on patients undergoing electron beam computer tomography, a diagnostic test for calcification of the arteries. PMID:19588455

In this work, we proposed a new strategy based on electrospray technique to prepare nanogels. Compared with other methods of preparing nanogels, electrospray technique is more simple and efficient. A biodegradable and multi-responsive poly(ether urethane) (PEU) was synthesized via a facile one-pot method and used as the electrospray material. By using electrospray technique, pH- and redox-responsive poly(ether urethane) nanogels were prepared. The morphologies of the electrospray nanoparticles before and after swelling were demonstrated to be spherical and uniform, as characterized by scanning electron microscope (SEM) and transmission electron microscopy (TEM). Dynamic light scattering (DLS) results showed that the mean hydrodynamic diameter of nanogels was about 500nm. The pH- and redox-sensitive behaviors of nanogels were studied with DLS and TEM. In acidic media the nanogels dissociated, while in the presence of GSH the nanogels degraded. The nanogels suspension was stored at 4°C and was stable without aggregation for at least 30 days. Doxorubicin (DOX) can be further loaded into the poly(ether urethane) nanogels. The electrospray nanogels can change the release rate of loaded drug in response to pH and GSH stimuli. PMID:26859119

Normal phase liquid chromatography is a common mode for chiral separations. Many chiral amines are used as drugs or are important intermediates for drug synthesis. Electrospray ionization mass spectrometry is well known for its high sensitivity. However, when using normal phase liquid chromatography, electrospray ionization is hampered by the poor ionization efficiency of analytes from organic eluents. Continuous-flow extractive desorption electrospray ionization, which introduces the eluents through a hypodermic needle into the electrospray plume is demonstrated here for its success to interface normal phase liquid chromatography to mass spectrometry detection. Such an approach was shown to be as or more sensitive than ultraviolet detection for a selected set of aromatic amine-functionalized enantiomers. Also demonstrated is the direct infusion of cell extracts to monitor phospholipids from three different bacterial cells. Despite their presence in non-electrospray-ionization-friendly extraction solvents, continuous-flow extractive desorption electrospray ionization enabled the sensitive detection of phospholipids and the ability to tune ion forms through incorporation of different spray modifiers. PMID:24923254

This work shows the potential of emulsion electrospraying of proteins using food-grade emulsions for the microencapsulation and enhanced protection of a model thermosensitive hydrophobic bioactive. Specifically, gelatin, a whey protein concentrate (WPC) and a soy protein isolate (SPI) were compared as emulsion stabilizers and wall matrices for encapsulation of α-linolenic acid. In a preliminary stage, soy bean oil was used as the hydrophobic component for the implementation of the emulsion electrospraying process, investigating the effect of protein type and emulsion protocol used (i.e. with or without ultrasound treatment) on colloidal stability. This oil was then substituted by the ω-3 fatty acid and the emulsions were processed by electrospraying and spray-drying, comparing both techniques. While the latter resulted in massive bioactive degradation, electrospraying proved to be a suitable alternative, achieving microencapsulation efficiencies (MEE) of up to ∼70%. Although gelatin yielded low MEEs due to the need of employing acetic acid for its processing by electrospraying, SPI and WPC achieved MEEs over 60% for the non-sonicated emulsions. Moreover, the degradation of α-linolenic acid at 80°C was significantly delayed when encapsulated within both matrices. Whilst less than an 8% of its alkene groups were detected after 27h of thermal treatment for free α-linolenic acid, up to 43% and 67% still remained intact within the electrosprayed SPI and WPC capsules, respectively. PMID:26674243

Although nanofibers fabricated by electrospinning have been attracting wide interest, the production of colloids by electrospraying has not much studied so far. We have developed a simple method for the production of core-shell colloids with high uniformity by means of the coaxial electrospray. Contrary to usual coaxial setup, the inner nozzle was set to touch the inside wall of the outer nozzle for reproducible production. A polymer solution for the core was introduced through the outer nozzle and another solution for the shell was provided through the inner nozzle. The structure of the colloids was dependent on the polymer concentration, relative feed ratio between the polymer solutions. Especially, core-shell structured colloids are our primary interest due to their promising uses in drug-delivery systems, cosmetics, and food industries. This talk will present the production of core-shell colloids consisting of two polymer components.

An electrospray ion source and method of operation includes the application of pulsed voltage to prevent electrolysis of analytes with a low electrochemical potential. The electrospray ion source can include an emitter, a counter electrode, and a power supply. The emitter can include a liquid conduit, a primary working electrode having a liquid contacting surface, and a spray tip, where the liquid conduit and the working electrode are in liquid communication. The counter electrode can be proximate to, but separated from, the spray tip. The power system can supply voltage to the working electrode in the form of a pulse wave, where the pulse wave oscillates between at least an energized voltage and a relaxation voltage. The relaxation duration of the relaxation voltage can range from 1 millisecond to 35 milliseconds. The pulse duration of the energized voltage can be less than 1 millisecond and the frequency of the pulse wave can range from 30 to 800 Hz.

Recently a new electrospray ionization interface for capillary electrophoresis-mass spectroscopy (CE-MS) has been developed. The interface uses a sheath flow of liquid to make electrical contact at the CZE terminus, thus defining both the CZE and electrospray field gradients. Ions created by the ESI process are sampled through a 1 mm nozzle into a region mechanically pumped at 50 L/s using a single-stage roots blower. The ions entering this region are sampled through a 2 mm dia skimmer orifice located 0.5 cm behind the nozzle orifice. Ions passing through the skimmer enter a radio frequency focusing quadrupole. This region is pumped by a cryopump. A mixture of four quaternary phosphonium salts is used to illustrate capillary electrophoresis separations with mass spectroscopy and their uses. 2 figs.

The disintegration of liquid drops with low electrical conductivity and subject to an electric field is investigated both theoretically and experimentally. This disintegration takes place through the development of a conical cusp that eventually ejects an ultrathin liquid ligament. A first tiny drop is emitted from the end of this ligament. Due to its exceptionally small size and large electric charge per unit volume, that drop has been the object of relevant recent studies. In this paper, universal scaling laws for the diameter and electric charge of the first issued droplet are proposed and validated both numerically and experimentally. Our analysis shows how charge relaxation is the mechanism that differentiates the onset of electrospray, including the first droplet ejection, from the classical steady cone-jet mode. In this way, our study identifies when and where charge relaxation and electrokinetic phenomena come into play in electrospray, a subject of live controversy in the field. PMID:27581554

A new quantitative contained-electrospray (ES) process is described here that employs a movable ES emitter to control the reactivity of charged microdroplets by varying their exposure time with acid vapor. The method allows elimination of ion suppression effects caused by the presence of various surface active compounds that coelute with the analyte. For mixtures, contained-ESI mass spectrometric analysis produces relative ion intensities that reflect the true concentrations of analytes in solution. The mechanism for this effect has been elucidated and ascribed to the generation of fine initial droplets in the presence of a high abundance of protons; together, these two factors eliminate competition for charge and space during ion formation. Examples of analytes tested include steroids, phospholipids, phosphopeptides, and sialylated glycans. At least 1 order of magnitude improvement in detection limits, sensitivity, and accuracy of detection was observed when compared to conventional electrospray. PMID:26437455

Microcapsules with fluid-core in viscoelastic shell is interesting partially because of their unusual elasticity/rigidity. Electrospray technique, more flexible and scalable than traditional bulk and microfluidic emulsification, was used to generate spherical microcapsules. In particular, sodium alginate fine droplets generated by electrospray was surface cross-linked by either Ca(II) or chitosan to form polyelectrolyte microcapsules. By adjusting the needle inner diameter, concentration of sodium alginate, and applied voltage, we can control the droplet size to the designated range. Furthermore, we can tune the thickness and thereby rigidity/elasticity of the viscoelastic shell by adjusting the residence time of microcapsules in gelation solution to control the rigidity/elasticity of microcapsules. These polyelectrolyte microcapsules were subject to the osmotic pressure of synthetic water-soluble polymers, such as poly(ethylene glycol), with progressively lower concentration to observe their osmotic swelling behavior.

A reversed-phase high-performance liquid chromatography/electrospray ionisation mass spectrometry (HPLC/ESI-MS) method has been developed to conclusively differentiate the epimers betamethasone and dexamethasone and various esterification products (betamethasone and dexamethasone 21-acetate, betamethasone and dexamethasone 21-phosphate, betamethasone 17-valerate, betamethasone 21-valerate and betamethasone 17,21-dipropionate) in counterfeit drugs. Good separation with baseline resolution of all epimers or isomers was obtained on a Zorbax Eclipse XDB or Luna C8 column, using a step gradient with mobile phases of 0.05 M ammonium acetate and acetonitrile. Betamethasones can also be distinguished by the relative abundance of their m/z 279 ion in the positive electrospray tandem mass spectra. The LC/MS or LC/MS/MS method developed was successfully applied to the analysis of drug product samples, i.e. creams and tablets. PMID:15052579

Electrospray ionization followed by collision-induced dissociation in a quadrupole ion trap mass spectrometer of mixtures of deprotonated phosphatidyldiacylglycerols afforded a group of three diagnostic ions of convenient abundance for each phosphatidyldiacylglycerol (PG) present in the mixture. Thus, it was possible to determine unmistakably the identity and substitution positions (sn-1 or sn-2) for both acyl groups of each PG present in the mixture. The method also allows the study of isomeric mixtures of PG and mixtures containing minor amounts of some PG from crude extracts of Lactobacillus acidophillus. The present results improve those of previous studies using fast atom bombardment and electrospray ionization tanden mass spectrometry, in which it was reported that it was possible to differentiate the identity and position of the sn-2 acyl substituent only by the presence of one ion, with variable abundance. PMID:11180636

Negative electrospray ionization/MS enabled rapid, specific, and selective screening for unique polar components at parts per million concentrations in commercial hydrocarbon products without extensive sample preparation, separation, chromatography, or quantitation. Commercial fuel types were analyzed with this method, including kerosene, jet fuel, white gas, charcoal lighter fluid, on-road and off-road diesel fuels, and various grades and brands of gasolines. The different types of fuels produced unique and relatively simple spectra. These analyses were then applied to hydrocarbon samples from a large, long-term fuel spill. Although the alkane, isoprenoid, and alkylcyclohexane portions began to biodegrade or weather, the polar components in these samples remained relatively unchanged. The type of fuel involved was readily identified by negative electrospray ionization/MS. This is an abstract of a paper presented at the 230th ACS National Meeting (Washington, DC 8/28/2005-9/1/2005).

We describe a novel strategy combining photocrosslinking and HPLC-based electrospray ionization mass spectrometry to identify UV crosslinked DNA-protein complexes. Eco RI DNA methyltransferase modifies the second adenine within the recognition sequence GAATTC. Substitution of 5-iodouracil for the thymine adjacent to the target base (GAATTC) does not detectably alter the DNA-protein complex. Irradiation of the 5-iodouracil-substituted DNA-protein complex at various wavelengths was optimized, with a crosslinking yield >60% at 313 nm after 1 min. No protein degradation was observed under these conditions. The crosslinked DNA-protein complex was further analyzed by electrospray ionization mass spectrometry. The total mass is consistent with irradiation-dependent covalent bond formation between one strand of DNA and the protein. These preliminary results support the possibility of identifying picomole quantities of crosslinked peptides by similar strategies. PMID:9421528

A methodusingliquid chromatography-electrospray mass spectrometry (LC-(ESI)MS) for the simultaneous determination of three macrolides (tylosin, spiramycin and tilmicosin) in poultry muscle has been developed. The drugs were extracted with EDTA McIlvaine buffer, filter through celite 545 and the extracts were cleaned up by SPE Oasis HLB cartridge. Separation was carried out in end-capped silica-based C18 column and mobile phases containing trifluoroacetic acid-acetonitrile with a binary gradient system at a flow rate 0.5 ml/min. Detection was performed by single mass spectrometry with electrospray ionization in the positive mode. Several parameters affecting the mass spectra were studied. Chicken samples from the market were analyzed to check the residue of macrolide antibiotics.

A system for sampling a surface includes a surface sampling probe comprising a solvent liquid supply conduit and a distal end, and a sample collector for suspending a sample collection liquid adjacent to the distal end of the probe. A first electrode provides a first voltage to solvent liquid at the distal end of the probe. The first voltage produces a field sufficient to generate electrospray plume at the distal end of the probe. A second electrode provides a second voltage and is positioned to produce a plume-directing field sufficient to direct the electrospray droplets and ions to the suspended sample collection liquid. The second voltage is less than the first voltage in absolute value. A voltage supply system supplies the voltages to the first electrode and the second electrode. The first electrode can apply the first voltage directly to the solvent liquid. A method for sampling for a surface is also disclosed.

The disintegration of liquid drops with low electrical conductivity and subject to an electric field is investigated both theoretically and experimentally. This disintegration takes place through the development of a conical cusp that eventually ejects an ultrathin liquid ligament. A first tiny drop is emitted from the end of this ligament. Due to its exceptionally small size and large electric charge per unit volume, that drop has been the object of relevant recent studies. In this paper, universal scaling laws for the diameter and electric charge of the first issued droplet are proposed and validated both numerically and experimentally. Our analysis shows how charge relaxation is the mechanism that differentiates the onset of electrospray, including the first droplet ejection, from the classical steady cone-jet mode. In this way, our study identifies when and where charge relaxation and electrokinetic phenomena come into play in electrospray, a subject of live controversy in the field. PMID:27581554

Desorption electrospray ionization mass spectrometry (DESI-MS) is a recent advance in the field of analytical chemistry. This review surveys the development of liquid sample DESI-MS (LS-DESI-MS), a variant form of DESI-MS that focuses on fast analysis of liquid samples, and its novel analy-tical applications in bioanalysis, proteomics, and reaction kinetics. Due to the capability of directly ionizing liquid samples, liquid sample DESI (LS-DESI) has been successfully used to couple MS with various analytical techniques, such as microfluidics, microextraction, electrochemistry, and chromatography. This review also covers these hyphenated techniques. In addition, several closely related ionization methods, including transmission mode DESI, thermally assisted DESI, and continuous flow-extractive DESI, are briefly discussed. The capabilities of LS-DESI extend and/or complement the utilities of traditional DESI and electrospray ionization and will find extensive and valuable analytical application in the future. PMID:27145689

In this work, two different technologies (electrospraying and nanospray drying) were evaluated for the encapsulation of folic acid using both a whey protein concentrate (WPC) matrix and a commercial resistant starch. The morphology of the capsules, molecular organization of the matrices upon encapsulation, encapsulation efficiency, and stability of the folic acid within the capsules under different storage conditions and upon thermal exposure were studied. Results showed that spherical nano-, submicro- and microcapsules were obtained through both techniques, although electrospraying led to smaller capsule sizes and to an enhanced control over their size distribution. Greater encapsulation efficiency was observed using WPC as encapsulating matrix, probably related to interactions between the protein and folic acid which favoured the incorporation of the bioactive. The best results in terms of bioactive stabilization in the different conditions assayed were also obtained for the WPC capsules, although both materials and encapsulation techniques led to improved folic acid stability, especially under dry conditions. PMID:25172691

Desorption electrospray ionization mass spectrometry (DESI-MS) is a recent advance in the field of analytical chemistry. This review surveys the development of liquid sample DESI-MS (LS-DESI-MS), a variant form of DESI-MS that focuses on fast analysis of liquid samples, and its novel analy-tical applications in bioanalysis, proteomics, and reaction kinetics. Due to the capability of directly ionizing liquid samples, liquid sample DESI (LS-DESI) has been successfully used to couple MS with various analytical techniques, such as microfluidics, microextraction, electrochemistry, and chromatography. This review also covers these hyphenated techniques. In addition, several closely related ionization methods, including transmission mode DESI, thermally assisted DESI, and continuous flow–extractive DESI, are briefly discussed. The capabilities of LS-DESI extend and/or complement the utilities of traditional DESI and electrospray ionization and will find extensive and valuable analytical application in the future.

Capillary electrophoresis has been used in conjunction with electrospray mass spectrometry using both full-scan and selected ion monitoring modes to supply as much information as possible about the venom of Dendroaspis polylepis polylepis (Black Mamba). As an example of the application of capillary electrophoresis/electrospray mass spectrometry (CE/ESI/MS) to the analysis of a complex mixture of small proteins, we have analyzed the venom of Dendroaspis polylepis polylepis using the combined techniques. Both full-scan and selected ion monitoring modes were employed. CE/ESI/MS provides a rapid and extremely sensitive method for molecular weight determination, particularly when selected ion monitoring is employed. It has been utilized to provide sequence confirmation for those toxins which have already been described in the literature. Our methodology indicates the presence of at least 70 peptides in the molecular weight range 6000-9000. PMID:8354229

Disposable plastic electrospray chips are particularly attractive for the automated analysis of organic compounds and organometallic compounds. Automated multi-track chip-based infusion electrospray mass spectrometry of low molecular weight compounds using an eight-channel plastic chip is presented. For that purpose, the commercial interface of a triple quadrupole linear ion trap was modified. A dual-channel plastic microchip, where two physically separated channels arrive very close to each other at the chip tip, was used to perform lock-mass accurate mass measurements on a quadrupole-time-of-flight instrument. The same chip was used to demonstrate the formation of an organometallic complex in solution on the chip tip. Furthermore, the potential to control the flow rate of each channel individually, which opens new possibilities in the study of supramolecular complexes, is discussed. PMID:20065514

Mass analysis is demonstrated for the detection of sub-microgram quantities of explosive samples on a metallic surface at atmospheric pressure using laser electrospray mass spectrometry (LEMS). A non-resonant femtosecond duration laser pulse vaporizes native samples for subsequent electrospray ionization and transfer into a time-of-flight mass spectrometer. LEMS was used to detect 2,3-dimethyl-2,3-dinitrobutane (DMNB), 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), 3,4,8,9,12,13-hexaoxa-1,6-diazabicyclo[4.4.4]tetradecane (HMTD), and 3,3,6,6,9,9-hexamethyl-1,2,4,5,7,8-hexaoxacyclononane (TATP) deposited on a steel surface. LEMS was also used to directly analyze composite propellant materials containing an explosive to determine the molecular composition of the explosive pellets at atmospheric pressure. PMID:20486263

The response of many previously low-detectable or undetectable compounds in electrospray ionization mass spectrometry (ESI-MS) has been enhanced by the addition of a simple, homemade needle into the traditional ESI interface. The needle located between the ESI emitter and the ion sweep cone (inlet of the detector) would ionize those neutral gaseous compounds, formed during electrospray, by a corona discharge process. The mobile phases, ESI parameters and positions of the needle were investigated and optimized. Several groups of compounds and herbal extracts were tested using the homemade set-up. Both the results of the flow injection and the hyphenated MS analyses showed significant enhancement effects of our homemade needle. The advantages of the proposed method include low cost, simplicity and practicality. PMID:23364279

The technique of fusing, or bonding, individual microchannel plate (MCP) stacks together offers the possibility of improving the uniformity of MCP stack operating characteristics and provides a convenient monolithic format. Here, the effectiveness of bonded MCP stacks and stacks of MCPs with curved surfaces is investigated to determine if MCP requirements for future astrophysical detectors can be achieved. The results show that both configurations give superior MCP performance characteristics. However, some problems remain with regard to the fabrication of bonded MCP stacks resulting in poor flat field characteristics and increased background.

RATIONALE: When measuring extremely wide isotope ratios (= 1 x 109) accelerator mass spectrometry (AMS) is the instrument of choice, however it requires an anion for injection into the tandem accelerator. Since many elements do not have positive electronegativities they do not form stable negative atomic ions, and hence are not compatible for isotope ratio measurement using AMS. Thus new approaches for forming anions are sought; fluoroanions are particularly attractive because fluorine is monoisotopic, and thus will not have overlapping isobars with the isotope of interest. METHODS: An approach is described for making zirconium fluoroanions using the fluorinating ionic liquid (IL) 1-ethyl-3-methylimidazolium fluorohydrogenate, which was used to generate abundant [ZrF5-] using electrospray ionization. The IL was dissolved in acetonitrile, combined with a dilute solution of either Zr4+ or ZrO2+, and then electrosprayed. Mass analysis and collision induced dissociation were conducted using a time-of-flight mass spectrometer. Cluster structures were predicted using density functional theory calculations. RESULTS: The fluorohydrogenate IL solutions generated abundant [ZrF5-] starting from solutions of both Zr4+ and ZrO2+. The mass spectra also contained IL-bearing cluster ions, whose compositions indicated the presence of [ZrF6]2- in solution, a conclusion supported by the structural calculations. Rinsing out the zirconium-IL solution with acetonitrile decreased the IL clusters, but enhanced [ZrF5]-, which was sorbed by the polymeric electrospray supply capillary, and then released upon rinsing. This reduced the ion background in the mass spectrum. CONCLUSIONS: The fluorohydrogenate-IL solutions are a facile way to form zirconium fluoroanions in the gas phase using electrospray. The approach has potential as a source of fluoroanions for injection into an AMS, which would enable high-sensitivity measurement of minor zirconium isotopes, and benefits from the absence of

It is not an exaggeration to say that much of chemistry involves ions in solution. A technique which allows for ions to be transferred from solution into the gas phase and subsequently analyzed by mass spectrometric detection would be of importance. If structural information, representative of the solution chemistry could be gained from these gas-phase ions, this would also be important. Electrospray mass spectrometry (ES-MS) is such a technique.

A new apparatus has been constructed that combines electrospray ionization with a quadrupole mass filter, hexapole ion trap, and velocity-map imaging. The purpose is to record photoelectron images of isolated chromophore anions. To demonstrate the capability of our instrument we have recorded the photodetachment spectra of isolated deprotonated phenol and indole anions. To our knowledge, this is the first time that the photodetachment energy of the deprotonated indole anion has been recorded.

Positive ion electrospray ionization mass spectra of polypeptides are usually obtained from solutions that are acidified and therefore contain relatively high concentrations of anions. The present study describes an investigation of the effects of these ubiquitous anions on the positive ion electrospray ionization mass spectra of peptides and proteins. Certain anionic species in the spray solutions were observed to cause a marked decrease in the net average charge of peptide and protein ions in the mass spectra compared to the average charge measured in the absence of these anions. This charge neutralization effect was found to depend solely on the nature of the anionic species and was independent of the source of the anion (acid or salt), with the propensity for neutralization following the order: CCl3COO- > CF3COO- > CH3COO- approximately Cl-. A mechanism for the observed charge reduction effect is proposed that involves two steps. The first step occurs in solution, where an anion pairs with a positively charged basic group on the peptide. The second step occurs during the process of desolvation or in the gas phase, where the ion pair dissociates to yield the neutral acid and the peptide with reduced charge state. The different propensities for charge neutralization of the different anionic species is presumed to reflect the avidity of the anion-peptide interaction. These findings demonstrate that any attempt to correlate the distribution of charge states observed on proteins in the gas phase (by positive ion electrospray ionization mass spectrometry) with the net charge residing on the protein in solution will require that the described anion effect be taken into account. In addition, it appears that some control over the distribution of charge states on peptides and protein ions can be exercised by an appropriate choice of anion in the electrospray solution. PMID:7978296

The processes that cause the failure of sheathless electrospray ionization (ESI) emitters, based on different kinds of gold coatings on fused-silica capillaries, are described and explained. The methods chosen for this study include electrochemical methods, ICPMS analysis of the electrolytes used, SEM studies, and electrospray experiments. Generally, the failure occurs by loss of the conductive coating. It is shown that emitters with sputter-coated gold lose their coatings because of mechanical stress caused by the gas evolution accompanying water oxidation or reduction. Emitters with gold coatings on top of adhesion layers of chromium and nickel alloy withstand this mechanical stress and have excellent durability when operating as cathodes. When operating as anodes, the adhesion layer is electrochemically dissolved through the gold film, and the gold film then flakes off. It is shown that the conductive coating behaves as a cathode even in the positive electrospray mode when the magnitude of a superimposed reductive electrophoretic current exceeds that of the oxidative electrospray current. Fairy-dust coatings developed in our laboratory (see Barnidge, D. R.; etal.Anal. Chem. 1999, 71, 4115-4118,) bygluing gold dust onto the emitter, are unaffected by the mechanical stress due to gas evolution. When oxidized, the fairy-dust coatings show an increased surface roughness and decreased conductivities due to the formation of gold oxide. The resistance of this oxide layer is however negligible in comparison with that of the gas phase in ESI. Furthermore, since no flaking and only negligible electrochemical etching of gold was found, practically unlimited emitter lifetimes may be achieved with fairy-dust coatings. PMID:11605837

An approach to exploiting curve-to-curve dependencies in order to achieve high data compression is presented. One of the approaches to date of along curve compression through use of cubic spline approximation is taken and extended by investigating the additional compressibility achievable through curve-to-curve structure exploitation. One of the models under investigation is reported on.

The viability of single and coaxial electrospray techniques to encapsulate model peptide-angiotensin II into near mono-dispersed spherical, nanocarriers comprising N-octyl-O-sulphate chitosan and tristearin, respectively, was explored. The stability of peptide under controlled electric fields (during particle generation) was evaluated. Resulting nanocarriers were analysed using dynamic light scattering and electron microscopy. Cell toxicity assays were used to determine optimal peptide loading concentration (~1 mg/ml). A trout model was used to assess particle behaviour in vivo. A processing limit of 20 kV was determined. A range of electrosprayed nanoparticles were formed (between 100 and 300 nm) and these demonstrated encapsulation efficiencies of ~92 ± 1.8%. For the single needle process, particles were in matrix form and for the coaxial format particles demonstrated a clear core-shell encapsulation of peptide. The outcomes of in vitro experiments demonstrated triphasic activity. This included an initial slow activity period, followed by a rapid and finally a conventional diffusive phase. This was in contrast to results from in vivo cardiovascular activity in the trout model. The results are indicative of the substantial potential for single/coaxial electrospray techniques. The results also clearly indicate the need to investigate both in vitro and in vivo models for emerging drug delivery systems. PMID:26449446

Studies of the gas phase ion chemistry of triply charged metal ions, M(3+) = Sc(3+), Y(3+), La(3+), Ce(3+), and Yb(3+), were made by electrospray and laser spray. Triply charged ion ligand complexes, M(3+)(ligand)(n) were produced in the gas phase by electrospray and laser spray for the following ligands; glucose; sucrose; raffinose; cyclodextrin; ginsenoside Rb(1); dimethyl sulfoxide (DMSO) and hexamethylphosphoramide (HMPA). The ion evaporation mechanism must be invoked to explain the transfer of more surface active ions (e.g., NH(4)(+)(H(2)O)(n)) in solution to the gas phase, while the transfer of low surface active ions (e.g., La(3+)(sucrose)(n)) may be explained by the charged residue model. In general, the laser spray gives stronger ion signals than electrospray for aqueous and water/methanol solutions. The laser spray is found to be more suitable for the observation of ions with larger solvation energies (e.g., Sc(3+)(DMSO)(n)). These results may be due to the enrichment of the sample concentration by the selective vaporization of the volatile solvent on the tip of the stainless steel capillary and also to the finer droplet formation caused by the laser irradiation. Copyright 1999 John Wiley & Sons, Ltd. PMID:10523765

A microfabricated fluidic device was developed for the automated real-time analysis of individual cells using capillary electrophoresis (CE) and electrospray ionization-mass spectrometry (ESI-MS). The microfluidic structure incorporates a means for rapid lysis of single cells within a free solution electrophoresis channel, where cellular constituents were separated, and an integrated electrospray emitter for ionization of separated components. The eluent was characterized using mass spectrometry. Human erythrocytes were used as a model system for this study. In this monolithically integrated device, cell lysis occurs at a channel intersection using a combination of rapid buffer exchange and an increase in electric field strength. An electroosmotic pump is incorporated at the end of the electrophoretic separation channel to direct eluent to the integrated electrospray emitter. The dissociated heme group and the alpha and beta subunits of hemoglobin from individual erythrocytes were detected as cells continuously flowed through the device. The average analysis throughput was approximately 12 cells per minute, demonstrating the potential of this method for high-throughput single cell analysis. PMID:20058879

Biological removal of organic sulfur from petroleum feedstocks offers an attractive alternative to conventional thermochemical treatment due to the mild operating conditions afforded by the biocatalyst. Electro-spray bioreactors were investigated for use in desulfurization due to their reported operational cost savings relative to mechanically agitated reactors and their capability of forming emulsions < 5 {micro}m. Here, the rates dibenzothiophene (DBT) oxidation to 2-hydroxybiphenyl (2-HBP) in hexadecane, by Rhodococcus sp. IGTS8 are compared in the two reactor systems. Desulfurization rates ranged from 1.0 and 5.0 mg 2-HBP/(dry g cells-h), independent of the reactor employed. The batch stirred reactor was capable of forming a very fine emulsion in the presence of the biocatalyst IGTS8, similar to that formed in the electro-spray reactors, presumably due to the fact that the biocatalyst produces its own surfactant. While electro-spray reactors did not prove to be advantageous for the IGTS8 desulfurization system, it may prove advantageous for systems which do not produce surface-active bioagents in addition to being mass transport limited.

A microfabricated fluidic device was developed for the automated real-time analysis of individual cells using capillary electrophoresis (CE) and electrospray ionization-mass spectrometry (ESI-MS). The microfluidic structure incorporates a means for rapid lysis of single cells within a free solution electrophoresis channel where cellular constituents were separated and an integrated electrospray emitter for ionization of separated components. The eluent was characterized using mass spectrometry. Human erythrocytes were used as a model system for this study. In this monolithically integrated device, cell lysis occurs at a channel intersection using a combination of rapid buffer exchange and an increase in electric field strength. An electroosmotic pump is incorporated at the end of the electrophoretic separation channel to direct eluent to the integrated electrospray emitter. The dissociated heme group and the α and β subunits of hemoglobin from individual erythrocytes were detected as cells continuously flowed through the device. The average analysis throughput was approximately 12 cells per minute demonstrating the potential of this method for high-throughput single cell analysis. PMID:20058879

Biodegradable particles are extremely useful in the development of novel drug delivery systems. Recent studies have suggested that morphology can influence the mechanisms of drug delivery in many ways. In the present study, biodegradable microparticles with different morphologies were prepared from poly(L‑lactide) (PLA) using the electrospraying technique. The microparticles were then systematically examined by scanning using an electron microscope. The results revealed that the preparation of drug-loaded microspheres through electrospraying is a simple and efficient method, and the processing parameters, such as polymer molecular weight, concentration, surfactant and solvent play an important role in obtaining high quality microcarriers. The association between microcarrier morphology and the processing parameters used was also investigated. Rifampin-loaded PLA microspheres were also prepared according to the above-mentioned model. Our data demonstrate that the drug release from PLA microspheres can be sustained in vitro for over 60 h. Our study focused on obtaining electrosprayed medicated microparticles from complex polyester particles. Further studies are required to explore the potential commercial use of these microparticles. PMID:25955135

Polarization-induced electrospray ionization (PI-ESI) is a simple technique for instant generation of gas-phase ions directly from a microliter-sized droplet for mass spectrometric analysis. A sample droplet was placed over a dielectric substrate and in proximity (2-3 mm) to the inlet of a mass spectrometer. Owing to the polarization effect induced by the high electric field provided by the mass spectrometer, the droplet was polarized and the electrospray was generated from the apex of the droplet. The polarization-induced electrospray could last for tens of seconds, which was sufficiently long to monitor fast reactions occurring within few seconds. Thus, we demonstrated the feasibility of using the droplet-based PI-ESI MS for the online monitoring of fast reactions by simply mixing two droplets (5-10 μL) containing reactants on a dielectric substrate placed in front of a mass spectrometer applied with a high voltage (-4500 V). Schiff base reactions and oxidation reactions that can generate intermediates/products within a few seconds were selected as the model reactions. The ionic reaction species generated from intermediates and products can be simultaneously monitored by PI-ESI MS in real time. We also used this approach to selectively detect acetone from a urine sample, in which acetone was derivatized in situ. In addition, the possibility of using this approach for quantitative analysis of acetone from urine samples was examined. PMID:27590551

Ambient ionization methods for mass spectrometry have enabled the in situ and in vivo analysis of biological tissues and cells. When an etched optical fiber is used to deliver laser energy to a sample in laser ablation electrospray ionization (LAESI) mass spectrometry, the analysis of large single cells becomes possible. However, because in this arrangement the ablation plume expands in three dimensions, only a small portion of it is ionized by the electrospray. Here we show that sample ablation within a capillary helps to confine the radial expansion of the plume. Plume collimation, due to the altered expansion dynamics, leads to greater interaction with the electrospray plume resulting in increased ionization efficiency, reduced limit of detection (by a factor of ~13, reaching 600 amol for verapamil), and extended dynamic range (6 orders of magnitude) compared to conventional LAESI. This enhanced sensitivity enables the analysis of a range of metabolites from small cell populations and single cells in the ambient environment. This technique has the potential to be integrated with flow cytometry for high-throughput metabolite analysis of sorted cells. PMID:23445532

Abstract. Recent developments in multimodal imaging and image-guided therapy requires multilayered microparticles that encapsulate several imaging and therapeutic agents in the same carrier. However, commonly used microencapsulation processes have multiple limitations such as low encapsulation efficiency and loss of bioactivity for the encapsulated biological cargos. To overcome these limitations, we have carried out both experimental and theoretical studies on coaxial electrospray of multilayered microparticles. On the experimental side, an improved coaxial electrospray setup has been developed. A customized coaxial needle assembly combined with two ring electrodes has been used to enhance the stability of the cone and widen the process parameter range of the stable cone-jet mode. With this assembly, we have obtained poly(lactide-co-glycolide) microparticles with fine morphology and uniform size distribution. On the theoretical side, an instability analysis of the coaxial electrified jet has been performed based on the experimental parameters. The effects of process parameters on the formation of different unstable modes have been studied. The reported experimental and theoretical research represents a significant step toward quantitative control and optimization of the coaxial electrospray process for microencapsulation of multiple drugs and imaging agents in multimodal imaging and image-guided therapy. PMID:23864011